Colorant compositions

ABSTRACT

Disclosed are colorant compounds of the formula 
                         
wherein R, R 1 , R 2 , R 3 , and R 4  each, independently of the others, is an alkyl group, an aryl group, an arylalkyl group, or an alkylaryl group, and wherein R, R 1 , R 2 , R 3 , and R 4  each can be joined to a phenyl moiety to form a ring, each R′ a , R′ b , and R′ c , independently of the others, is a halogen atom, an alkyl group, an alkoxy group, a nitrile group, a nitro group, an amide group, or a sulfonamide group, z1, z2, and z3 each, independently of the others, is an integer of 0, 1, 2, 3, or 4, n is an integer representing the number of carbon atoms in each repeat alkylene oxide unit, x is an integer representing the number of repeat alkylene oxide units, D is an anion, and g is the charge on the anion, wherein said colorant has no more than one —OH, —SH, or primary or secondary amino group per molecule.

This application is a divisional of U.S. application Ser. No.10/422,895, filed Apr. 24, 2003, now U.S. Pat. No. 7,094,812 thedisclosure of which is totally incorporated herein by reference.

CROSS-REFERENCES TO COPENDING APPLICATIONS

Application U.S. Ser. No. 10/422,755, now U.S. Pat. No. 7,034,185, filedApr. 24, 2003, entitled “Colorant Precursor Compositions,” with thenamed inventors Jeffery H. Banning, Donald R. Titterington, and CliffordR. King, the disclosure of which is totally incorporated herein byreference, discloses colorant precursor compounds of the formula

wherein R is an alkyl group, an aryl group, an arylalkyl group, or analkylaryl group, and wherein R can be joined to the phenyl moiety toform a ring, each R′, independently of the others, is a halogen atom, analkyl group, an alkoxy group, a nitrile group, a nitro group, an amidegroup, or a sulfonamide group, z is an integer of 0, 1, 2, 3, or 4, n isan integer representing the number of carbon atoms in each repeatalkylene oxide unit, and x is an integer representing the number ofrepeat alkylene oxide units, wherein said colorant precursor has no morethan one —OH, —SH, or primary or secondary amino group per molecule.

Application U.S. Ser. No. 10/422,897, now U.S. Pat. No. 6,790,267, filedApr. 24, 2003, entitled “Colorant Compositions,” with the namedinventors Jeffery H. Banning, Donald R. Titterington, and Clifford R.King, the disclosure of which is totally incorporated herein byreference, discloses colorant compounds of the formula

wherein R is an alkyl group, an aryl group, an arylalkyl group, or analkylaryl group, and wherein R can be joined to the phenyl moiety toform a ring, each R′, independently of the others, is a halogen atom, analkyl group, an alkoxy group, a nitrile group, a nitro group, an amidegroup, or a sulfonamide group, z is an integer of 0, 1, 2, 3, or 4, n isan integer representing the number of carbon atoms in each repeatalkylene oxide unit, x is an integer representing the number of repeatalkylene oxide units, and A and B each, independently of the other, arehydrogen atoms, halogen atoms, tertiary amino groups, imine groups,ammonium groups, cyano groups, pyridine groups, pyridinium groups, ethergroups, ester groups, amide groups, sulfate groups, sulfonate groups,sulfide groups, sulfoxide groups, phosphine groups, phosphonium groups,phosphate groups, nitrile groups, mercapto groups, nitro groups, sulfonegroups, acyl groups, azo groups, cyanato groups, alkyl groups, alkoxygroups, aryl groups, aryloxy groups, arylalkyl groups, arylalkyloxygroups, alkylaryl groups, or alkylaryloxy groups, wherein said coloranthas no more than one —OH, —SH, or primary or secondary amino group permolecule.

application U.S. Ser. No. 10/422,742, now U.S. Pat. No. 6,764,541, filedApr. 24, 2003, entitled “Colorant Compositions,” with the namedinventors Jeffery H. Banning, Donald R. Titterington, and Clifford R.King, the disclosure of which is totally incorporated herein byreference, discloses colorant composition of the formula

wherein R is an alkyl group, an aryl group, an arylalkyl group, or analkylaryl group, and wherein R can be joined to the phenyl moiety toform a ring, R′ is an aromatic- or heteroaromatic-containing group, eachR_(a), independently of the others, is a halogen atom, an alkyl group,an alkoxy group, a nitrile group, a nitro group, an amide group, or asulfonamide group, w is an integer of 0, 1, 2, 3, or 4, n is an integerrepresenting the number of carbon atoms in each repeat alkylene oxideunit, and x is an integer representing the number of repeat alkyleneoxide units, wherein said colorant has no more than one —OH, —SH, orprimary or secondary amino group per molecule.

Copending application U.S. Ser. No. 11/496,612 filed concurrentlyherewith, with the named inventors Jeffery H. Banning, Donald R.Titterington, and Clifford R. King, the disclosure of which is totallyincorporated herein by reference, discloses phase change inks containingcolorant compounds of the formula

wherein R, R₁, R₂, R₃, and R₄ each, independently of the others, is analkyl group, an aryl group, an arylalkyl group, or an alkylaryl group,and wherein R, R₁, R₂, R₃, and R₄ each can be joined to a phenyl moietyto form a ring, each R′_(a), R′_(b), and R′_(c), independently of theothers, is a halogen atom, an alkyl group, an alkoxy group, a nitrilegroup, a nitro group, an amide group, or a sulfonamide group, z1, z2,and z3 each, independently of the others, is an integer of 0, 1, 2, 3,or 4, n is an integer representing the number of carbon atoms in eachrepeat alkylene oxide unit, x is an integer representing the number ofrepeat alkylene oxide units, D is an anion, and g is the charge on theanion, wherein said colorant has no more than one —OH, —SH, or primaryor secondary amino group per molecule.

Copending application U.S. Ser. No. 11/496,231 filed concurrentlyherewith, with the named inventors Jeffery H. Banning, Donald R.Titterington, and Clifford R. King, the disclosure of which is totallyincorporated herein by reference, discloses phase change inks containingcolorant compounds comprising two or more moieties of the formula

wherein R, R₁, R₂, R₃, and R₄ each, independently of the others, is analkyl group, an aryl group, an arylalkyl group, or an alkylaryl group,and wherein R, R₁, R₂, R₃, and R₄ each can be joined to a phenyl moietyto form a ring, each R′_(a), R′_(b), and R′_(c), independently of theothers, is a halogen atom, an alkyl group, an alkoxy group, a nitrilegroup, a nitro group, an amide group, or a sulfonamide group, z1, z2,and z3 each, independently of the others, is an integer of 0, 1, 2, 3,or 4, n is an integer representing the number of carbon atoms in eachrepeat alkylene oxide unit, x is an integer representing the number ofrepeat alkylene oxide units, D is an anion, and g is the charge on theanion, wherein said moieties each contain no —OH groups, —SH groups, orprimary or secondary amino groups, said moieties being linked by acentral atom or group of atoms or bonded to a polymer.

BACKGROUND OF THE INVENTION

The present invention is directed to specific colorant compounds and toink compositions containing these colorant compounds. More specifically,the present invention is directed to specific triarylmethane colorantcompounds, and to ink compositions containing these colorant compounds.One embodiment of the present invention is directed to a colorantcompound of the formula

wherein R, R₁, R₂, R₃, and R₄ each, independently of the others, is analkyl group, an aryl group, an arylalkyl group, or an alkylaryl group,and wherein R, R₁, R₂, R₃, and R₄ each can be joined to a phenyl moietyto form a ring, each R′_(a), R′_(b), and R′_(c), independently of theothers, is a halogen atom, an alkyl group, an alkoxy group, a nitrilegroup, a nitro group, an amide group, or a sulfonamide group, z1, z2,and z3 each, independently of the others, is an integer of 0, 1, 2, 3,or 4, n is an integer representing the number of carbon atoms in eachrepeat alkylene oxide unit, x is an integer representing the number ofrepeat alkylene oxide units, D is an anion, and g is the charge on theanion, wherein said colorant has no more than one —OH, —SH, or primaryor secondary amino group per molecule. Another embodiment of the presentinvention is directed to a compound comprising two or more moieties ofthe formula

wherein R, R₁, R₂, R₃, and R₄ each, independently of the others, is analkyl group, an aryl group, an arylalkyl group, or an alkylaryl group,and wherein R, R₁, R₂, R₃, and R₄ each can be joined to a phenyl moietyto form a ring, each R′_(a), R′_(b), and R′_(c), independently of theothers, is a halogen atom, an alkyl group, an alkoxy group, a nitrilegroup, a nitro group, an amide group, or a sulfonamide group, z1, z2,and z3 each, independently of the others, is an integer of 0, 1, 2, 3,or 4, n is an integer representing the number of carbon atoms in eachrepeat alkylene oxide unit, x is an integer representing the number ofrepeat alkylene oxide units, D is an anion, and g is the charge on theanion, wherein said moieties each contain no —OH groups, —SH groups, orprimary or secondary amino groups, said moieties being linked by acentral atom or group of atoms or bonded to a polymer. Yet anotherembodiment of the present invention is directed to a phase change inkcomprising a phase change carrier and a colorant compound comprising oneor more moieties of the formula

wherein R, R₁, R₂, R₃, and R₄ each, independently of the others, is analkyl group, an aryl group, an arylalkyl group, or an alkylaryl group,and wherein R, R₁, R₂, R₃, and R₄ each can be joined to a phenyl moietyto form a ring, each R′_(a), R′_(b), and R′^(c), independently of theothers, is a halogen atom, an alkyl group, an alkoxy group, a nitrilegroup, a nitro group, an amide group, or a sulfonamide group, z1, z2,and z3 each, independently of the others, is an integer of 0, 1, 2, 3,or 4, n is an integer representing the number of carbon atoms in eachrepeat alkylene oxide unit, x is an integer representing the number ofrepeat alkylene oxide units, D is an anion, and g is the charge on theanion, wherein, when the colorant compound contains exactly one of themoieties, the moiety contains no more than one —OH, —SH, or primary orsecondary amino group per molecule, and when the colorant compoundcontains more than one of the moieties, said moieties each contain no—OH groups, —SH groups, or primary or secondary amino groups.

In general, phase change inks (sometimes referred to as “hot melt inks”)are in the solid phase at ambient temperature, but exist in the liquidphase at the elevated operating temperature of an ink jet printingdevice. At the jet operating temperature, droplets of liquid ink areejected from the printing device and, when the ink droplets contact thesurface of the recording substrate, either directly or via anintermediate heated transfer belt or drum, they quickly solidify to forma predetermined pattern of solidified ink drops. Phase change inks havealso been used in other printing technologies, such as gravure printing,as disclosed in, for example, U.S. Pat. No. 5,496,879 and German PatentPublications DE 4205636AL and DE 4205713AL, the disclosures of each ofwhich are totally incorporated herein by reference.

Phase change inks for color printing typically comprise a phase changeink carrier composition which is combined with a phase change inkcompatible colorant. In a specific embodiment, a series of colored phasechange inks can be formed by combining ink carrier compositions withcompatible subtractive primary colorants. The subtractive primarycolored phase change inks can comprise four component dyes, namely,cyan, magenta, yellow and black, although the inks are not limited tothese four colors. These subtractive primary colored inks can be formedby using a single dye or a mixture of dyes. For example, magenta can beobtained by using a mixture of Solvent Red Dyes or a composite black canbe obtained by mixing several dyes. U.S. Pat. No. 4,889,560, U.S. Pat.No. 4,889,761, and U.S. Pat. No. 5,372,852, the disclosures of each ofwhich are totally incorporated herein by reference, teach that thesubtractive primary colorants employed can comprise dyes from theclasses of Color Index (C.I.) Solvent Dyes, Disperse Dyes, modified Acidand Direct Dyes, and Basic Dyes. The colorants can also includepigments, as disclosed in, for example, U.S. Pat. No. 5,221,335, thedisclosure of which is totally incorporated herein by reference. U.S.Pat. No. 5,621,022, the disclosure of which is totally incorporatedherein by reference, discloses the use of a specific class of polymericdyes in phase change ink compositions.

Phase change inks have also been used for applications such as postalmarking, industrial marking, and labelling.

Phase change inks are desirable for ink jet printers because they remainin a solid phase at room temperature during shipping, long term storage,and the like. In addition, the problems associated with nozzle cloggingas a result of ink evaporation with liquid ink jet inks are largelyeliminated, thereby improving the reliability of the ink jet printing.Further, in phase change ink jet printers wherein the ink droplets areapplied directly onto the final recording substrate (for example, paper,transparency material, and the like), the droplets solidify immediatelyupon contact with the substrate, so that migration of ink along theprinting medium is prevented and dot quality is improved.

Compositions suitable for use as phase change ink carrier compositionsare known. Some representative examples of references disclosing suchmaterials include U.S. Pat. No. 3,653,932, U.S. Pat. No. 4,390,369, U.S.Pat. No. 4,484,948, U.S. Pat. No. 4,684,956, U.S. Pat. No. 4,851,045,U.S. Pat. No. 4,889,560, U.S. Pat. No. 5,006,170, U.S. Pat. No.5,151,120, U.S. Pat. No. 5,372,852, U.S. Pat. No. 5,496,879, EuropeanPatent Publication 0187352, European Patent Publication 0206286, GermanPatent Publication DE 4205636AL, German Patent Publication DE 4205713AL,and PCT Patent Application WO 94/04619, the disclosures of each of whichare totally incorporated herein by reference. Suitable carrier materialscan include paraffins, microcrystalline waxes, polyethylene waxes, esterwaxes, fatty acids and other waxy materials, fatty amide containingmaterials, sulfonamide materials, resinous materials made from differentnatural sources (tall oil rosins and rosin esters, for example), andmany synthetic resins, oligomers, polymers, and copolymers.

U.S. Pat. No. 5,864,002 (Stephens et al.), the disclosure of which istotally incorporated herein by reference, discloses a method ofproviding for manufacturing a colored polymer resin having the steps of:(a) blending a disazo colorant into a mixture of monomers, the coloranthaving a poly(oxyalkylene) substituent comprising from 2 to 200 alkyleneoxide residues, bonded to each end of the disazo chromophore, thepoly(oxyalkylene) substituent having a nucleophilic terminal group whichis capable of reacting with at least a portion of the monomers; (b)providing conditions under which the monomers and disazo colorantpolymerize to form a colored polymer resin.

U.S. Pat. No. 5,591,833 (Hines et al.), the disclosure of which istotally incorporated herein by reference, discloses colorants andcompositions useful as a fugitive or permanent colorant for a variety ofsubstrates, or as intermediates for their manufacture, and having one ormore improved properties of enhanced aqueous washability, compatibilitywith and non-extractibility from thermoplastic resins, or reactivitywith resins having reactive functionality, said composition having theformula C(Z)₁₋₈ wherein C is the residue of a reactant having from 1 to8 nucleophilic site residues to which the Z moieties are attached; saidZ moieties containing at least about 60 weight percent ofpoly(oxyalkylene) which comprises (a) at least one glycidol residuesegment of 2 to 6 glycidol residues attached to a nucleophilic site ofC, wherein said poly(oxyalkylene) contains a total of from 2 to 20glycidol residues, (b) and wherein said poly(oxyalkylene) furthercontains the residues of one or more other epoxide reactants of ethyleneoxide (EO), propylene oxide (PO), or butylene oxide (BO), or mixturesthereof, wherein said poly(oxyalkylene) contains a total of from about10 to about 600 of said EO, PO, or BO residues, or mixtures thereof, atleast about 75 mole percent of which are EO residues, (c) and with theprovisions that the ratio of the total of —O—PO— and —O—BO— linkages ofall glycidol residues to the total of all functional oxy linkages ofsaid glycidol residues is less than one, and the molar ratio of EOresidues to glycidol residues is from 4 to 75.

U.S. Pat. No. 5,290,921 (Moody et al.), the disclosure of which istotally incorporated herein by reference, discloses primary hydroxylenhanced colorants having markedly improved reactivities in e.g.,polyurethane foams for imparting permanent coloring thereto, thecolorants having the formula C-(Z)¹⁻⁴ wherein C is an azo, methine, orazamethine chromogen and Z is a poly(oxyalkylene) moiety comprising (1)at least two (A) units independently selected from those of the formulae—CH₂CH(O-T)CH₂O— or —CH₂CH(O-T)CH₂O-T and (2) from none to about 200 (B)units of the formula (—RO—) wherein R is straight or branched chainhydrocarbon of 2 to 4 carbons, T is a moiety of the formula—CH₂CH(R₁)—O—(RO)₀₋₄₀—CH₂CH₂OH wherein R₁ is selected from unsubstitutedor substituted alkyl, aryl, alkenyloxyalkyl, alkoxyalkyl, oraryloxyalkyl, and wherein the A units comprise at least 0.5 percent ofthe total A+B units.

U.S. Pat. No. 5,108,460 (Hines et al.), the disclosure of which istotally incorporated herein by reference, discloses azo chromophoreshaving polyoxyalkylene substituents that are linked together by acovalent bond or by an intervening connecting group to form dimers ortrimers. The polyoxyalkylene substituents are straight or branched chainpolymers primarily of ethylene oxide which make the dimer and trimercolorants useful as fugitive tints.

U.S. Pat. No. 5,082,938 (Kluger et al.), the disclosure of which istotally incorporated herein by reference, discloses enhanced branchedchain hydroxyl compounds of formula Y-(Z)₁₋₆ wherein Y is the residue ofa nucleophile devoid of conjugated divalent linking moieties, and each Zis a poly(oxyalkylene) moiety having a molecular weight of from about200 to 10,000 and containing at least one glycidol residue, wherein atleast one of the primary oxy sites of said glycidol residue is linkedpreferably directly to a first epoxide residue of three or more carbons,and wherein said first epoxide residue is linked through a secondary oxysite preferably directly to a second epoxide reside having a primaryterminal hydroxyl.

U.S. Pat. No. 5,043,013 (Kluger et al.), the disclosure of which istotally incorporated herein by reference, discloses a washable aqueousink composition having a viscosity of from about 1.0 to about 6.0centipoise and containing from about 10 to about 50 percent by weight ofone or more polymeric colorants of the formula{R₁ ((RO)_(a)—Y)_(b)}_(c)wherein X is a polar group such as sulfonic acids, sulfonic acid salts,sulfonamides, sulfonates or the like; R is alkylene; Y is H, alkanoyl,carbamoyl, or the like; R₁ is nitrogen, oxygen, sulfur, or asulfur-containing divalent linking group; a is an integer of from six toabout forty; b and c are each independently selected from one or two; dis an integer of from one to four; the product of (a) (b) (c) is aninteger of from 6 to about 40; and CHROM is a chromophore such as nitro,nitroso, monoazo, disazo and trisazo, diarylmethane, triarylmethane,xanthane, acridine, methine, thiazole, indamine, azine, oxazine, oranthraquinone, wherein the (RO)_(a) moiety is bonded to a carbocyclicaromatic ring of the (CHROM) through R₁.

U.S. Pat. No. 4,751,254 (Kluger et al.), the disclosure of which istotally incorporated herein by reference, discloses a process forcoloring polyurethane resins during the production of same with reactivecolorants derived from polyalkoxytrifluoroaniline intermediates. Thesecolorants impart increased brightness in shade for both aromatic andheteroaromatic derivatives and increased resistance to stannousoctanoate catalyst over conventional polymeric colorants derived forheteroaromatic compounds. These colorants have the structure

wherein R₁ is selected from H, a lower alkyl group containing from 1 toabout 10 carbon atoms, CH₂Cl, CH₂OH, phenyl, or

where R₆ is H or a lower alkyl group containing from 1 to about 9 carbonatoms; R₂ is selected from OH, NH₂, or SH; R₃ is selected from a loweralkyl group containing from 1 to about 9 carbon atoms, cyanoalkyl,acetoxyalkyl, or

where R₁ and R₂ are as given above; R₄ is H, CF₃, a lower alkyl groupcontaining from 1 to about 9 carbon atoms, Cl, or Br and n is 0 or aninteger from 1 to about 125. R₅ is an aromatic or heteroaromaticcontaining group, said colorants being resistant to stannous octanoate,being characterized as having improved brightness and which havefunctionality through reactive substituents thereof.

U.S. Pat. No. 4,658,064 (Moore et al.), the disclosure of which istotally incorporated herein by reference, discloses a compound of theformula

wherein R₁ is selected from alkyl, halide, or alkoxy; R₂ is selectedfrom H or alkyl; Y is a number of from 2 to about 200; and Z is selectedfrom H or

where W is alkyl.

U.S. Pat. No. 4,594,454 (Moore et al.), the disclosure of which istotally incorporated herein by reference, discloses a compound of theformula

wherein R₁ is selected from alkyl, halide, or alkoxy; R₂ is selectedfrom H or alkyl; Y is a number of from 2 to about 200; and Z is selectedfrom H or

where W is alkyl.

U.S. Pat. No. 4,400,320 (Keller et al.), the disclosure of which istotally incorporated herein by reference, discloses fugitive tints whichare characterized by the formula

where R is selected from meta-toluidene, meta-amino phenol, aniline, ordimethoxy aniline, A is selected from N, O, S, or CO₂; the alkylenegroup of the alkyleneoxy constituent contains from 2 to about 4 carbonatoms; n is an integer of from 2 to about 300; m is 1 when A is O, S, orCO₂, and 2 when A is N; x is an integer of from 1 to about 5; and theproduct of n times m times x (n°m°x) is from 2 to about 400. Alsodisclosed is a process for preparing alkyleneoxy fugitive tints.

U.S. Pat. No. 4,284,729 (Cross et al.), the disclosure of which istotally incorporated herein by reference, discloses a process forcoloring thermosetting resins, made by polyaddition reaction of anucleophile with an electrophile, with a polymeric liquid reactivecoloring agent suitable for incorporation in the resin with theformation of covalent bonds, said coloring agent having the formulaR-(polymeric constituent-X)_(n)wherein R is an organic dyestuff radical; the polymeric constituent isselected from polyalkylene oxides and copolymers of polyalkylene oxidesin which the alkylene moiety of the polymeric constituent contains 2 ormore carbon atoms and such polymeric constituent has a molecular weightof from about 44 to about 1500; and n is an integer of from 1 to about6; and X is selected from —OH, —NH₂, and —SH, said coloring agent beingadded in an amount sufficient to provide coloration of saidthermosetting resin.

U.S. Pat. No. 4,132,840 (Hugl et al.), the disclosure of which istotally incorporated herein by reference, discloses polyurethaneplastics that are dyed with dyestuffs of the formula

wherein R₁ denotes hydrogen, halogen, optionally substituted C₁-C₄alkyl, optionally substituted C₁-C₄ alkoxy, and optionally substitutedC₁-C₄ alkylcarbonylamino and R₂ denotes hydrogen, optionally substitutedC₁-C₄ alkyl, and optionally substituted C₁-C₄ alkoxy, while A and Bdenote optionally branched alkylene chains which can be identical ordifferent and preferably have 2 to 6 carbon atoms, with formation ofcovalent bonds, in that the dyestuffs are added before or during thepolyaddition reaction to the reaction mixture of polyol andpolyisocyanate or to one of the components.

U.S. Pat. No. 3,994,835 (Wolf et al.), the disclosure of which istotally incorporated herein by reference, discloses dispersions ofdyestuffs which contain at least one free amino or hydroxyl groupcapable of reacting with isocyanates under the conditions ofpolyaddition and liquids in which the dyes are soluble to an extent lessthan 2 percent which are suitable for the production of coloredpolyurethane foams. The dye dispersions can be added before or duringthe polyaddition reaction.

U.S. Pat. No. 5,270,363 (Kluger et al.), the disclosure of which istotally incorporated herein by reference, discloses a colorant fornatural or synthetic resinous or polymeric materials, having the formulaA-(SO₂—N(R₂)—Y)₁₋₄ wherein R₂ is selected for example from hydrogen,methyl, cyclohexyl, phenyl or Y; A is a nonionic metallophthalocyaninechromophore which can be substituted for example with halogen, alkyl,alkoxy, alkylthio, or aryloxy; Y is a poly(oxyalkylene) moietycontaining at least three monomeric units or mixtures thereof of theformula (—RO—) wherein each R is straight or branched alkylene of 1 to 4carbons or mixtures thereof, up to about 20 mole percent of saidmonomeric units may be connected by one or more linking groups such asalkyleneoxy, —NH—, or —NHCONH—, and wherein Y can be terminated byhydrogen, or by at branch substituents, containing 1 to 3 groups ormoieties selected from alkyl, cycloalkyl, acyl, or aryl; wherein any ofthe above recited hydrocarbon groups, moieties or substituents maythemselves be substituted with up to four substituents selected, forexample, from alkyl, halogen, mercapto, alkoxycarbonyl, hydroxy, alkoxy,or the like; and wherein each aliphatic hydrocarbon portion or moiety ofthe groups, moieties or substituents recited above contains from 1 to 20carbons.

U.S. Pat. No. 4,912,203 (Kluger et al.), the disclosure of which istotally incorporated herein by reference, discloses thiophene basedcolorants useful for coloring thermoset resins such as polyurethanesbeing of the formula

wherein R₁, R₂, and R₃ are selected from halogen, carboxylic acid,alkanoyl, aryloyl, carbocyclic forming polymethylene chains, alkyl,aryl, cyano, thioalkyl, dithioalkyl, thioaryl, dithioaryl, thiocyano,carboxyalkyl, carboxyaryl, amidoalkyl, amidodialkyl, amidoaryl,amidodiaryl, oxyalkyl, thioamidoalkyl, thioamidodialkyl, or hydrogenwhen an adjacent group is isobutyryl; R₄, R₅, and R₇ are selected fromhydrogen alkyl, oxyalkyl, sulfonamidoalkyl, sulfonamidoaryl, amidoalkyl,amidodialkyl, amidoaryl, amidodiaryl, halogen, thioalkyl, and thioaryl;and R₈ and R₉ are selected from polyalkylene oxide, copolymers ofpolyalkylene oxides, and hydroxyalkylenes.

U.S. Pat. No. 4,846,846 (Rekers et al.), the disclosure of which istotally incorporated herein by reference, discloses a process forcoloring polyurethane resins made by a polyaddition reaction of a polyoland an isocyanate which comprises adding to the reaction mixture beforeor during the polyaddition reaction a reactive coloring agent suitablefor incorporation in the resin with the formation of covalent bonds,said coloring agent having the formula

in which R₁ and R₂ are independently selected from an alkyl group havingfrom 1 to about 12 carbon atoms, X is —CH₂—, a and a′ are integers from1 to about 6, and Y and Y′ are independently selected from polymericunits of hydroxy alkylenes or alkylene oxide monomers selected fromethylene oxide, propylene oxide, butylene oxide, cyclohexene oxide, orglycidol, b and b′ are independently either 0 or 1, and Z and Z′ arereactive groups independently selected from —OH, —NH₂, or —SH.

U.S. Pat. No. 4,507,407 (Kluger et al.), the disclosure of which istotally incorporated herein by reference, discloses a process ofcoloring polyurethane resins during the production of same with reactivecolorants having the formula

wherein R₁, R₂, R₃ are selected from halogen, carboxylic acid, alkanoyl,aryloyl, alkyl, aryl, cyano, sulfonylalkyl, sulfonylaryl, thioalkyl,thioaryl, sulfinylalkyl, sulfinylaryl, dithioalkyl, dithioaryl,thiocyano, amidoalkyl, amidodialkyl, oxyalkyl, oxyaryl, hydrogen,sulfonamidoalkyl, sulfonamidoaryl, sulfonamidodialkyl,sulfonamidodiaryl, carbocyclic forming polymethylene chains,sulfenamidoalkyl, sulfenamidodialkyl, sulfenamidoaryl,sulfenamidodiaryl, sulfinamidoalkyl, sulfinamidodialkyl,sulfinamidoaryl, sulfinamidodiaryl; and A is an organic dyestuff couplerthat is resistant to stannous octanoate and flame retardant compoundsand which has functionality through reactive substituents thereof.

U.S. Pat. No. 5,919,839 (Titterington et al.), the disclosure of whichis totally incorporated herein by reference, discloses colored waxesmade by reacting selected nucleophiles, including alcohol containingcolorants, with an isocyanate. A phase change ink is made by blendingthe colored wax with a clear ink carrier composition. The clear inkcarrier composition can be a fatty amide-based material and/or acombination of isocyanate-derived resins in which the order of additionof the isocyanate and the different nucleophiles can tailor thedistribution of di-urethane, mixed urethane/urea, and/or di-ureamolecules in the final resin product. The colored wax materials areuseful as ingredients with phase change ink carrier compositions to makephase change ink jet inks.

U.S. Pat. No. 5,456,725 (Bruhnke), the disclosure of which is totallyincorporated herein by reference, discloses a process for temporarilycoloring a polyamide substrate whereby a poly(oxyalkylene) substitutedmethine colorant is applied to the substrate followed by heating thesubstrate with superheated steam at a temperature of 250° F. or greater,which effectively decolorizes the methine colorant.

PCT Patent Application WO 97/13816, the disclosure of which is totallyincorporated herein by reference, discloses a colored material suitablefor use in a hot melt ink comprising a oligomeric hot melt ink jetvehicle formed of molecules having a backbone and at least one pendantside-chain. A dyestuff is reacted onto the backbone. The material ispreferably obtainable as the reaction product of an aliphatic oraromatic mono- or di-isocyanate and a hydroxyl group functional dyecomponent, and optionally one or more other suitable material. Suchsuitable materials include mono- and dihydric alcohols, primary andsecondary monoamines, functional amides, hydroxyl functional amines andhydroxyl containing components having a terminal unsaturated bond.

“Polymeric Colorants,” J. Miley, IUPAC Pure and Applied Chemistry, Vol.68, No. 7, p. 1423 (1996), the disclosure of which is totallyincorporated herein by reference, discloses specific examples ofpolymeric colorants and how they meet functional requirements.

While known compositions are suitable for their intended purposes, aneed remains for improved reactive triarylmethane colorants. Inaddition, a need remains for reactive triarylmethane colorants that areeasily purified. Further, a need remains for reactive triarylmethanecolorants that exhibit reduced toxicity. Additionally, a need remainsfor reactive triarylmethane colorants that are liquid at roomtemperature. There is also a need for reactive triarylmethane colorantsthat can be tailored for compatibility with various hydrophobic orhydrophilic applications. In addition, there is a need for reactivetriarylmethane colorants that, when reacted with polymers such aspolyurethanes, polyanhydrides, or the like, resist migration and/orsettling. Further, there is a need for reactive triarylmethane colorantsthat, when reacted with other materials, do not result in the formationof products of undesirably high molecular weight. Additionally, there isa need for reactive triarylmethane colorants that, when reacted withother materials, do not result in the formation of products withundesirable crosslinking. A need also remains for reactivetriarylmethane colorants that, when reacted with other materials, formproducts suitable for use in phase change ink compositions. In addition,a need remains for reactive triarylmethane colorants that, when reactedwith other materials, form products that, when incorporated into phasechange ink compositions, exhibit reduced precipitation of the colorantfrom the ink. Further, a need remains for reactive triarylmethanecolorants that, when reacted with other materials, form products thatwhen incorporated into phase change ink compositions, exhibit reducedclogging of printer heads and resulting printer failure.

SUMMARY OF THE INVENTION

The present invention is directed to a colorant compound of the formula

wherein R, R₁, R₂, R₃, and R₄ each, independently of the others, is analkyl group, an aryl group, an arylalkyl group, or an alkylaryl group,and wherein R, R₁, R₂, R₃, and R₄ each can be joined to a phenyl moietyto form a ring, each R′_(a), R′_(b), and R′_(c), independently of theothers, is a halogen atom, an alkyl group, an alkoxy group, a nitrilegroup, a nitro group, an amide group, or a sulfonamide group, z1, z2,and z3 each, independently of the others, is an integer of 0, 1, 2, 3,or 4, n is an integer representing the number of carbon atoms in eachrepeat alkylene oxide unit, x is an integer representing the number ofrepeat alkylene oxide units, D is an anion, and g is the charge on theanion, wherein said colorant has no more than one —OH, —SH, or primaryor secondary amino group per molecule. Another embodiment of the presentinvention is directed to a compound comprising two or more moieties ofthe formula

wherein R, R₁, R₂, R₃, and R₄ each, independently of the others, is analkyl group, an aryl group, an arylalkyl group, or an alkylaryl group,and wherein R, R₁, R₂, R₃, and R₄ each can be joined to a phenyl moietyto form a ring, each R′_(a), R′_(b), and R′_(c), independently of theothers, is a halogen atom, an alkyl group, an alkoxy group, a nitrilegroup, a nitro group, an amide group, or a sulfonamide group, z1, z2,and z3 each, independently of the others, is an integer of 0, 1, 2, 3,or 4, n is an integer representing the number of carbon atoms in eachrepeat alkylene oxide unit, x is an integer representing the number ofrepeat alkylene oxide units, D is an anion, and g is the charge on theanion, wherein said moieties each contain no —OH groups, —SH groups, orprimary or secondary amino groups, said moieties being linked by acentral atom or group of atoms or bonded to a polymer. Yet anotherembodiment of the present invention is directed to a phase change inkcomprising a phase change carrier and a colorant compound comprising oneor more moieties of the formula

wherein R, R₁, R₂, R₃, and R₄ each, independently of the others, is analkyl group, an aryl group, an arylalkyl group, or an alkylaryl group,and wherein R, R₁, R₂, R₃, and R₄ each can be joined to a phenyl moietyto form a ring, each R′_(a), R′_(b), and R′_(c), independently of theothers, is a halogen atom, an alkyl group, an alkoxy group, a nitrilegroup, a nitro group, an amide group, or a sulfonamide group, z1, z2,and z3 each, independently of the others, is an integer of 0, 1, 2, 3,or 4, n is an integer representing the number of carbon atoms in eachrepeat alkylene oxide unit, x is an integer representing the number ofrepeat alkylene oxide units, D is an anion, and g is the charge on theanion, wherein, when the colorant compound contains exactly one of themoieties, the moiety contains no more than one —OH, —SH, or primary orsecondary amino group per molecule, and when the colorant compoundcontains more than one of the moieties, said moieties each contain no—OH groups, —SH groups, or primary or secondary amino groups.

DETAILED DESCRIPTION OF THE INVENTION

The present invention is directed to a colorant of the formula

wherein R, R₁, R₂, R₃, and R₄ each, independently of the others, is analkyl group (including linear, branched, saturated, unsaturated, cyclic,and unsubstituted alkyl groups, and wherein hetero atoms, such asoxygen, nitrogen, sulfur, silicon, phosphorus, and the like either mayor may not be present in the alkyl group), in one embodiment with atleast 1 carbon atom, and in another embodiment with at least about 2carbon atoms, and in one embodiment with no more than about 50 carbonatoms, and in another embodiment with no more than about 48 carbonatoms, although the number of carbon atoms can be outside of theseranges, an aryl group (including unsubstituted and substituted arylgroups, and wherein hetero atoms, such as oxygen, nitrogen, sulfur,silicon, phosphorus, and the like either may or may not be present inthe aryl group), in one embodiment with at least about 5 carbon atoms,and in another embodiment with at least about 6 carbon atoms, and in oneembodiment with no more than about 50 carbon atoms, and in anotherembodiment with no more than about 48 carbon atoms, although the numberof carbon atoms can be outside of these ranges, an arylalkyl group(including unsubstituted and substituted arylalkyl groups, and whereinhetero atoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, andthe like either may or may not be present in either or both of the alkylportion and the aryl portion of the arylalkyl group), in one embodimentwith at least about 6 carbon atoms, and in another embodiment with atleast about 7 carbon atoms, and in one embodiment with no more thanabout 50 carbon atoms, and in another embodiment with no more than about48 carbon atoms, although the number of carbon atoms can be outside ofthese ranges, or an alkylaryl group (including unsubstituted andsubstituted alkylaryl groups, and wherein hetero atoms, such as oxygen,nitrogen, sulfur, silicon, phosphorus, and the like either may or maynot be present in either or both of the alkyl portion and the arylportion of the alkylaryl group), in one embodiment with at least about 6carbon atoms, and in another embodiment with at least about 7 carbonatoms, and in one embodiment with no more than about 50 carbon atoms,and in another embodiment with no more than about 48 carbon atoms,although the number of carbon atoms can be outside of these ranges,wherein the substituents on the substituted alkyl, aryl, arylalkyl, andalkylaryl groups can be (but are not limited to) halogen atoms, tertiaryamino groups, imine groups, ammonium groups, cyano groups, pyridinegroups, pyridinium groups, ether groups, ester groups, amide groups,sulfate groups, sulfonate groups, sulfide groups, sulfoxide groups,phosphine groups, phosphonium groups, phosphate groups, nitrile groups,mercapto groups, nitro groups, sulfone groups, acyl groups, azo groups,cyanato groups, and the like, as well as mixtures thereof, and whereintwo or more substituents can be joined together to form a ring, each R′,independently of the others, is a halogen atom, an alkyl group, analkoxy group, a nitrile group, a nitro group, an amide group, or asulfonamide group, z is an integer of 0, 1, 2, 3, or 4, n is an integerrepresenting the number of carbon atoms in each repeat alkylene oxideunit (the alkylene oxide units can each have different numbers of carbonatoms; for example, the polyalkylene oxide chain can comprise a mixtureof repeat ethylene oxide, propylene oxide, and/or butylene oxide units),and typically is from about 2 to about 18, and preferably from about 2to about 4, although the value of n can be outside of these ranges, andx is an integer representing the number of repeat alkylene oxide units,and typically is from about 2 to about 100, and preferably from about 5to about 20, although the value of x can be outside of these ranges,wherein said colorant has no more than one —OH, —SH, or —NHR″ group(i.e., primary or secondary amino group) per molecule, wherein R″ is ahydrogen atom, an alkyl group (including linear, branched, saturated,unsaturated, cyclic, and unsubstituted alkyl groups, and wherein heteroatoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, and thelike either may or may not be present in the alkyl group), in oneembodiment with at least 1 carbon atom, and in another embodiment withat least about 2 carbon atoms, and in one embodiment with no more thanabout 50 carbon atoms, and in another embodiment with no more than about48 carbon atoms, although the number of carbon atoms can be outside ofthese ranges, an aryl group (including unsubstituted and substitutedaryl groups, and wherein hetero atoms, such as oxygen, nitrogen, sulfur,silicon, phosphorus, and the like either may or may not be present inthe aryl group), in one embodiment with at least 5 carbon atoms, and inanother embodiment with at least about 6 carbon atoms, and in oneembodiment with no more than about 50 carbon atoms, and in anotherembodiment with no more than about 48 carbon atoms, although the numberof carbon atoms can be outside of these ranges, an arylalkyl group(including unsubstituted and substituted arylalkyl groups, and whereinhetero atoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, andthe like either may or may not be present in either or both of the alkylportion and the aryl portion of the arylalkyl group), in one embodimentwith at least about 6 carbon atoms, and in another embodiment with atleast about 7 carbon atoms, and in one embodiment with no more thanabout 50 carbon atoms, and in another embodiment with no more than about48 carbon atoms, although the number of carbon atoms can be outside ofthese ranges, such as benzyl or the like, or an alkylaryl group(including unsubstituted and substituted alkylaryl groups, and whereinhetero atoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, andthe like either may or may not be present in either or both of the alkylportion and the aryl portion of the alkylaryl group), in one embodimentwith at least about 6 carbon atoms, and in another embodiment with atleast about 7 carbon atoms, and in one embodiment with no more thanabout 50 carbon atoms, and in another embodiment with no more than about48 carbon atoms, although the number of carbon atoms can be outside ofthese ranges, such as tolyl or the like, and wherein the substituents onthe substituted alkyl, aryl, arylalkyl, and alkylaryl groups can be (butare not limited to) those indicated hereinabove for the R group.

If desired, various substituents (shown as R′_(a), R′_(b), and R′_(c)groups on the structure) can be present on the central phenyl moiety ofthe structure to affect the color of a colorant, such as a methinecolorant or a triarylmethane colorant, prepared from the precursormolecule. From 1 to 4 of such substituents can be present on each phenylring, which can be the same as each other or different from each other.Examples of such substituents include (but are not limited to) halogenatoms, such as fluorine, chlorine, bromine, and iodine, alkyl groups,typically with from 1 to about 25 carbon atoms, such as methyl, ethyl,and the like, alkoxy groups, typically with from 1 to about 25 carbonatoms, such as methoxy groups, ethoxy groups, and the like, nitrilegroups, nitro groups, amide groups, such as an acetamido group or thelike, including (but not limited to) those of the general formula

wherein R_(a) is a hydrogen atom, an alkyl group (including linear,branched, saturated, unsaturated, cyclic, and unsubstituted alkylgroups, and wherein hetero atoms, such as oxygen, nitrogen, sulfur,silicon, phosphorus, and the like either may or may not be present inthe alkyl group), in one embodiment with at least 1 carbon atom, and inanother embodiment with at least about 2 carbon atoms, and in oneembodiment with no more than about 50 carbon atoms, and in anotherembodiment with no more than about 48 carbon atoms, although the numberof carbon atoms can be outside of these ranges, an aryl group (includingunsubstituted and substituted aryl groups, and wherein hetero atoms,such as oxygen, nitrogen, sulfur, silicon, phosphorus, and the likeeither may or may not be present in the aryl group), in one embodimentwith at least 5 carbon atoms, and in another embodiment with at leastabout 6 carbon atoms, and in one embodiment with no more than about 50carbon atoms, and in another embodiment with no more than about 48carbon atoms, although the number of carbon atoms can be outside ofthese ranges, an arylalkyl group (including unsubstituted andsubstituted arylalkyl groups, and wherein hetero atoms, such as oxygen,nitrogen, sulfur, silicon, phosphorus, and the like either may or maynot be present in either or both of the alkyl portion and the arylportion of the arylalkyl group), in one embodiment with at least about 6carbon atoms, and in another embodiment with at least about 7 carbonatoms, and in one embodiment with no more than about 50 carbon atoms,and in another embodiment with no more than about 48 carbon atoms,although the number of carbon atoms can be outside of these ranges, suchas benzyl or the like, or an alkylaryl group (including unsubstitutedand substituted alkylaryl groups, and wherein hetero atoms, such asoxygen, nitrogen, sulfur, silicon, phosphorus, and the like either mayor may not be present in either or both of the alkyl portion and thearyl portion of the alkylaryl group), in one embodiment with at leastabout 6 carbon atoms, and in another embodiment with at least about 7carbon atoms, and in one embodiment with no more than about 50 carbonatoms, and in another embodiment with no more than about 48 carbonatoms, although the number of carbon atoms can be outside of theseranges, such as tolyl or the like, and wherein the substituents on thesubstituted alkyl, aryl, arylalkyl, and alkylaryl groups can be (but arenot limited to) those indicated hereinabove for the R group, such as anacetamido group or the like, sulfonamide groups, including (but notlimited to) those of the formula

wherein R_(b) is a hydrogen atom, an alkyl group (including linear,branched, saturated, unsaturated, cyclic, and unsubstituted alkylgroups, and wherein hetero atoms, such as oxygen, nitrogen, sulfur,silicon, phosphorus, and the like either may or may not be present inthe alkyl group), in one embodiment with at least 1 carbon atom, and inanother embodiment with at least about 2 carbon atoms, and in oneembodiment with no more than about 50 carbon atoms, and in anotherembodiment with no more than about 48 carbon atoms, although the numberof carbon atoms can be outside of these ranges, an aryl group (includingunsubstituted and substituted aryl groups, and wherein hetero atoms,such as oxygen, nitrogen, sulfur, silicon, phosphorus, and the likeeither may or may not be present in the aryl group), in one embodimentwith at least 5 carbon atoms, and in another embodiment with at leastabout 6 carbon atoms, and in one embodiment with no more than about 50carbon atoms, and in another embodiment with no more than about 48carbon atoms, although the number of carbon atoms can be outside ofthese ranges, an arylalkyl group (including unsubstituted andsubstituted arylalkyl groups, and wherein hetero atoms, such as oxygen,nitrogen, sulfur, silicon, phosphorus, and the like either may or maynot be present in either or both of the alkyl portion and the arylportion of the arylalkyl group), in one embodiment with at least about 6carbon atoms, and in another embodiment with at least about 7 carbonatoms, and in one embodiment with no more than about 50 carbon atoms,and in another embodiment with no more than about 48 carbon atoms,although the number of carbon atoms can be outside of these ranges, suchas benzyl or the like, or an alkylaryl-group (including unsubstitutedand substituted alkylaryl groups, and wherein hetero atoms, such asoxygen, nitrogen, sulfur, silicon, phosphorus, and the like either mayor may not be present in either or both of the alkyl portion and thearyl portion of the alkylaryl group), in one embodiment with at leastabout 6 carbon atoms, and in another embodiment with at least about 7carbon atoms, and in one embodiment with no more than about 50 carbonatoms, and in another embodiment with no more than about 48 carbonatoms, although the number of carbon atoms can be outside of theseranges, such as tolyl or the like, and wherein the substituents on thesubstituted alkyl, aryl, arylalkyl, and alkylaryl groups can be (but arenot limited to) those indicated hereinabove for the R group, or thelike.

It should be noted that the R, R₁, R₂, R₃, and R₄ groups can each,independently of the others, also be joined to one of the central phenylmoieties to form a ring; for example, compounds of the formulae

are within the scope of the above formula.

Materials of this formula can be prepared from a precursor of theformula

which can be prepared according to the following reaction scheme (inwhich, for purposes of simplicity, no R′ groups are shown):

More specifically, the terminal hydroxy group in the polyalkoxy anilineis first converted to an acetate group to protect this functionality insubsequent reaction steps. This conversion can be performed via anacetylation reaction, wherein the polyalkoxy aniline is first heated,typically to a temperature of from about 90 to about 150° C., althoughthe temperature can be outside of this range, and subjected to vacuum toremove water, and subsequently reacted with acetic anhydride, if desiredin the presence of an optional esterification catalyst, such as dibutyltin laurate, para-toluene sulfonic acid, 1-methylimidazole, or the like,as well as mixtures thereof, under reflux conditions, typically at atemperature of from about 90 to about 150° C., although the temperaturecan be outside of this range, and an inert atmosphere. The aceticanhydride typically, although not necessarily, is present in a slightmolar excess relative to the polyalkoxy aniline. Thereafter, excessacetic acid (generated as a reaction byproduct) and acetic anhydride canbe removed by vacuum distillation to yield the acetylated product.

The acetylated product is then admixed with a formulating agent, such asdimethyl formamide, N-methyl formamide (which can be prepared asdisclosed in, for example, Organic Synthesis Collective Volume 3, p 98,1955, John Wiley and Sons, ISBN 0 471 40953 7, the disclosure of whichis totally incorporated herein by reference), or the like, with theformylating agent typically, although not necessarily, present in amolar excess of from about 5 to about 20 percent, and cooled to about 0°C., followed by dropwise addition of POCl₃ in a molar excess amount attemperatures of no more than about 5° C., and subsequent warming to roomtemperature. Thereafter, the reaction mixture is heated, typically to atemperature of from about 50 to about 100° C., although the temperaturecan be outside of this range, and a base, such as sodium hydroxide,potassium hydroxide, calcium hydroxide, calcium oxide, mixtures thereof,or the like is added slowly, with the base typically present in a molarexcess of from about 1.1 moles of base per every one mole of acetylatedproduct to about 10 moles of base per every one mole of acetylatedproduct, although the amount can be outside of these ranges, followed byseparation of the acetylated and formylated product via a separatoryfunnel.

The acetylated and formylated product is then deprotected to convert theacetate end group back to a hydroxy group. The acetylated and formylatedproduct is admixed with a mixture of sodium hydroxide and potassiumhydroxide, with the sodium hydroxide/potassium hydroxide mixturetypically present in a molar excess of from about 1.1 moles of base perevery one mole of acetylated and formylated product to about 10 moles ofbase per every one mole of acetylated and formylated product, althoughthe amount can be outside of these ranges, and heated, typically to atemperature of from about 60 to about 120° C., although the temperaturecan be outside of these ranges, typically for a period of about 3 hours,although the time can be greater or lesser than this amount, followed byaddition of water until the cloud point is reached, i.e., when theacetylated and formylated product separates from the water (typically anamount of water on a molar basis that is from about 0.75 to about 3times as much water as acetylated and formylated product) and continuedheating, typically at a temperature of from about 60 to about 100° C.,although the temperature can be outside of this range. The productmixture is then allowed to phase separate, and the deprotectedformylated product can be recovered via a separatory funnel.

If desired, the cycle of admixing with 0.75 to 3 times as much water asproduct, heating, and separating can be repeated to remove salts to adesired level. If desired, vacuum can be employed for further removal ofwater from the product.

Starting materials of the formula

are commercially available from, for example Henkel Corporation,Mauldin, S.C. For example, a material of this formula wherein n is 2 andx is 10 is available. From the same company is also available as SO-7864a similar material wherein both ethylene oxide and propylene oxidegroups are randomly distributed through the polyalkylene oxide chain inan average molar ratio of about 3.5 moles of ethylene oxide groups to6.5 moles of propylene oxide groups. Materials of this formula can alsobe prepared by, for example, obtaining a commercially available anilineof the formula

and reacting it with an epoxide compound having the desired number ofcarbon atoms in the presence of a Lewis acid or a base. Morespecifically, if one wants, for example, a compound wherein n is 3(i.e., a polypropylene oxide substituted compound), one can react theaniline with an epoxide compound of the formula

If one wants a compound wherein n is 2 (i.e., a polyethylene oxidesubstituted compound), one can react the aniline with an epoxidecompound of the formula

The molar ratio of epoxide compound to N-alkyl aniline is such that thedesired number of repeat alkylene oxide units per N-alkyl anilinemolecule is obtained; for example, if it is desired to have a moleculewith an average of about 10 repeat alkylene oxide units (i.e., x=10),the molar ratio of epoxide compound to N-alkyl aniline is about 10:1.

The reaction can take place in the presence of a catalyst which iseither a base, such as potassium hydroxide or the like, or a Lewis acid,such as BF₃ etherate or the like. The catalyst is present in any desiredor effective amount, in one embodiment at least about 0.01 mole ofcatalyst per every one mole of aniline, in another embodiment at leastabout 0.05 mole of catalyst per every one mole of aniline, and in yetanother embodiment at least about 0.1 mole of catalyst per every onemole of aniline, and in one embodiment no more than about 0.3 mole ofcatalyst per every one mole of aniline, in another embodiment no morethan about 0.2 mole of catalyst per every one mole of aniline, and inyet another embodiment no more than about 0.1 mole of catalyst per everyone mole of aniline, although the relative amounts can be outside ofthese ranges.

Further information regarding these kinds of reactions is disclosed in,for example, Preparation I of U.S. Pat. No. 4,091,034, Example 1 of U.S.Pat. No. 4,167,510, Example I of U.S. Pat. No. 4,400,320, and Example 1Aof U.S. Pat. No. 5,290,921, the disclosures of each of which are totallyincorporated herein by reference.

The material of the formula

is then reacted with one or more suitable aniline compounds to form atriarylmethane colorant. Suitable aniline compounds include those of thegeneral formulae

wherein each R′_(b) and each R′_(c), independently of the other, havethe same definitions as R′_(a) and z2 and z3 each, independently of theother, have the same definitions as z1, wherein R₁, R₂, R₃, and R₄ each,independently of the others, is an alkyl group (including linear,branched, saturated, unsaturated, cyclic, and unsubstituted alkylgroups, and wherein hetero atoms, such as oxygen, nitrogen, sulfur,silicon, phosphorus, and the like either may or may not be present inthe alkyl group), in one embodiment with at least 1 carbon atom, and inanother embodiment with at least about 2 carbon atoms, and in oneembodiment with no more than about 50 carbon atoms, and in anotherembodiment with no more than about 48 carbon atoms, although the numberof carbon atoms can be outside of these ranges, an aryl group (includingunsubstituted and substituted aryl groups, and wherein hetero atoms,such as oxygen, nitrogen, sulfur, silicon, phosphorus, and the likeeither may or may not be present in the aryl group), in one embodimentwith at least about 5 carbon atoms, and in another embodiment with atleast about 6 carbon atoms, and in one embodiment with no more thanabout 50 carbon atoms, and in another embodiment with no more than about48 carbon atoms, although the number of carbon atoms can be outside ofthese ranges, an arylalkyl group (including unsubstituted andsubstituted arylalkyl groups, and wherein hetero atoms, such as oxygen,nitrogen, sulfur, silicon, phosphorus, and the like either may or maynot be present in either or both of the alkyl portion and the arylportion of the arylalkyl group), in one embodiment with at least about 6carbon atoms, and in another embodiment with at least about 7 carbonatoms, and in one embodiment with no more than about 50 carbon atoms,and in another embodiment with no more than about 48 carbon atoms,although the number of carbon atoms can be outside of these ranges, oran alkylaryl group (including unsubstituted and substituted alkylarylgroups, and wherein hetero atoms, such as oxygen, nitrogen, sulfur,silicon, phosphorus, and the like either may or may not be present ineither or both of the alkyl portion and the aryl portion of thealkylaryl group), in one embodiment with at least about 6 carbon atoms,and in another embodiment with at least about 7 carbon atoms, and in oneembodiment with no more than about 50 carbon atoms, and in anotherembodiment with no more than about 48 carbon atoms, although the numberof carbon atoms can be outside of these ranges, wherein the substituentson the substituted alkyl, aryl, arylalkyl, and alkylaryl groups can be(but are not limited to) halogen atoms, tertiary amino groups, iminegroups, ammonium groups, cyano groups, pyridine groups, pyridiniumgroups, ether groups, ester groups, amide groups, sulfate groups,sulfonate groups, sulfide groups, sulfoxide groups, phosphine groups,phosphonium groups, phosphate groups, nitrile groups, mercapto groups,nitro groups, sulfone groups, acyl groups, azo groups, cyanato groups,and the like, as well as mixtures thereof, and wherein two or moresubstituents can be joined together to form a ring.

The reaction takes place by reacting in one embodiment at least about0.9 part by mole, in another embodiment about 0.95 part by mole, and inyet another embodiment about 0.99 part by mole, and in one embodiment nomore than about 1 part by mole of a compound of the formula

and either from about 2 to about 2.05 parts by mole of a compound of theformula (in which, for purposes of simplicity, no R′ groups are shown)

or a mixture of compounds of the formulae (in which, for purposes ofsimplicity, no R′ groups are shown)

in any desired relative ratio with respect to each other, wherein thenumber of parts by mole of compound containing R₁ and R₂ plus the numberof parts by mole of compound containing R₃ and R₄ equals from about 2 toabout 2.05 in the presence of a mineral acid that promotes dehydration,such as sulfuric acid, phosphoric acid, or the like. The mineral acid ispresent in any desired or effective amount, in one embodiment at leastabout 1 mole of mineral acid per every one mole of compound of theformula

and in another embodiment at least about 1.5 moles of mineral acid perevery one mole of compound of the formula

and in one embodiment no more than about 3 moles of mineral acid perevery one mole of compound of the formula

and in another embodiment no more than about 2 moles of mineral acid perevery one mole of compound of the formula

although the relative amounts can be outside of these ranges.

The reactants are heated to any desired or effective temperature, in oneembodiment at least about 70° C., and in another embodiment at leastabout 80° C., and in one embodiment no more than about 100° C., and inanother embodiment no more than about 95° C., although the temperaturecan be outside of these ranges.

The reactants are allowed to react for any desired or effective periodof time, in one embodiment at least about 1 hour, and in anotherembodiment at least about 3 hours, and in one embodiment no more thanabout 24 hours, and in another embodiment no more than about 6 hours,although the period of time can be outside of these ranges.

The reaction proceeds in two steps, as follows (in which, for purposesof simplicity, no R′ groups are shown):

Any desired or effective oxidizing agent commonly employed to preparetriarylmethanes can be used, such as chloranil, hydrogen peroxide,benzoquinone, or the like, as well as mixtures thereof. The oxidizingagent is present in any desired or effective relative amount, in oneembodiment at least about 1 mole of oxidizing agent per every one moleof the leuco form of the colorant, and in one embodiment no more thanabout 5 moles of oxidizing agent per every one mole of the leuco form ofthe colorant, and in another embodiment no more than about 2 moles ofoxidizing agent per every one mole of the leuco form of the colorant,although the relative amounts can be outside of these ranges.

The oxidizing agent and the leuco form of the colorant are heated to anydesired or effective temperature, in one embodiment at least about 25°C., in another embodiment at least about 55° C., and in yet anotherembodiment at least about 100° C., and in one embodiment no more thanabout 125° C., in another embodiment no more than about 115° C., and inyet another embodiment no more than about 105° C., although thetemperature can be outside of these ranges.

The oxidizing agent and the leuco form of the colorant are allowed toreact for any desired or effective period of time, in one embodiment atleast about 5 minutes, in another embodiment at least about 30 minutes,and in yet another embodiment at least about 60 minutes, and in oneembodiment no more than about 12 hours, in another embodiment no morethan about 6 hours, and in yet another embodiment no more than about 2hours, although the period of time can be outside of these ranges.

The reaction product mixture can then be neutralized with a base, suchas NaOH or the like, and the salt layer can then be separated from theproduct layer. Optionally, the colorant can be subsequently washed withmore water to reduce the salt layer to the level desired.

The resulting triarylmethane colorant is of the formula

wherein each R′_(a), R′_(b), and R′_(c), independently of the others, isa halogen atom, an alkyl group, an alkoxy group, a nitrile group, anitro group, an amide group, or a sulfonamide group, z1, z2, and z3each, independently of the others, is an integer of 0, 1, 2, 3, or 4, n,and x are as defined hereinabove, D is an anion corresponding to themineral acid used in the reaction to synthesize the colorant, and grepresents the charge on the anion, typically being 1, 2, 3, 4, or thelike.

Colorants of the present invention can be reacted with various atoms,groups of atoms, monomers, oligomers, or polymers to form variouscolored monomers, oligomers, or polymers having covalently bondedthereto a colorant according to the present invention. Anotherembodiment of the present invention is directed to a compound comprisingtwo or more moieties of the formula

wherein R, R₁, R₂, R₃, and R₄ each, independently of the others, is analkyl group, an aryl group, an arylalkyl group, or an alkylaryl group,and wherein R, R₁, R₂, R₃, and R₄ each can be joined to a phenyl moietyto form a ring, each R′_(a), R′_(b), and R′_(c), independently of theothers, is a halogen atom, an alkyl group, an alkoxy group, a nitrilegroup, a nitro group, an amide group, or a sulfonamide group, z1, z2,and z3 each, independently of the others, is an integer of 0, 1, 2, 3,or 4, n is an integer representing the number of carbon atoms in eachrepeat alkylene oxide unit, x is an integer representing the number ofrepeat alkylene oxide units, D is an anion, and g is the charge on theanion, wherein said moieties each contain no —OH groups, —SH groups, orprimary or secondary amino groups, said moieties being linked by acentral atom or group of atoms or bonded to a polymer.

Examples of colored groups of atoms, monomers, oligomers, or polymerswhich can be prepared with the colorants of the present inventioninclude urethane isocyanate-derived monomers, oligomers, or polymers,urea isocyanate-derived monomers, oligomers, or polymers, urethane/ureaisocyanate-derived monomers, oligomers, or polymers, anhydride monomers,oligomers, or polymers, such as styrene-maleic anhydride monomers,oligomers, or polymers, ester/polyester monomers, oligomers, orpolymers, carbonate/polycarbonate monomers, oligomers, or polymers, andthe like. Colored urethane isocyanate-derived monomers, oligomers, orpolymers, urea isocyanate-derived monomers, oligomers, or polymers, andurethane/urea isocyanate-derived monomers, oligomers, or polymers havingcovalently bonded thereto a colorant according to the present inventionare generally the reaction product of a colorant according to thepresent invention and an isocyanate. Colored urethane isocyanate-derivedmonomers, oligomers, or polymers, urea isocyanate-derived monomers,oligomers, or polymers, and urethane/urea isocyanate-derived monomers,oligomers, or polymers having covalently bonded thereto a colorantaccording to the present invention can be prepared by, for example,processes such as those disclosed in U.S. Pat. No. 5,919,839; U.S. Pat.No. 3,994,835; U.S. Pat. No. 4,132,840; U.S. Pat. No. 4,751,254; U.S.Pat. No. 5,290,921; U.S. Pat. No. 5,270,363; U.S. Pat. No. 4,912,203;U.S. Pat. No. 4,846,846; U.S. Pat. No. 4,507,407; U.S. Pat. No.4,284,729; U.S. Pat. No. 5,864,002; PCT Patent Application WO 97/13816;J. H. Saunders and K. C. Frisch's “Polyurethanes Part I, Chemistry”published by Interscience of New York, N.Y. in 1962; and Olin Chemicals'Luxate® IM isophorone diisocyanate technical product information sheet;the disclosures of each of which are totally incorporated herein byreference. Further information on isocyanate-derived resins is disclosedin, for example, U.S. Pat. No. 5,782,966; U.S. Pat. No. 5,750,604; U.S.Pat. No. 5,827,918; U.S. Pat. No. 5,830,942; U.S. Pat. No. 5,994,453;U.S. Pat. No. 6,180,692; U.S. Pat. No. 6,018,005; U.S. Pat. No.6,028,138; U.S. Pat. No. 6,048,925; U.S. Pat. No. 6,057,399; and U.S.Pat. No. 5,783,658; the disclosures of each of which are totallyincorporated herein by reference.

For example, a monoisocyanate reacts with an alcohol to form a urethaneas follows:

Diisocyanates react similarly; for example, isophorone diisocyanatereacts with two moles of alcohol to form a diurethane as follows:

Monomeric, oligomeric, and polymeric materials can be prepared whenHO—R_(b) is a colorant or colorant precursor according to the presentinvention.

Examples of suitable isocyanates include monoisocyanates, diisocyanates,triisocyanates, copolymers of a diisocyanate, copolymers of atriisocyanate, polyisocyanates (having more than three isocyanatefunctional groups), and the like, as well as mixtures thereof. Examplesof monoisocyanates include octadecylisocyanate; hexadecylisocyanate;octylisocyanate; butyl and t-butylisocyanate; cyclohexyl isocyanate;adamantyl isocyanate; ethylisocyanatoacetate; ethoxycarbonylisocyanate;phenylisocyanate; alphamethylbenzyl isocyanate; 2-phenylcyclopropylisocyanate; benzylisocyanate; 2-ethylphenylisocyanate;benzoylisocyanate; meta and para-tolylisocyanate; 2-, 3-, or4-nitrophenylisocyanates; 2-ethoxyphenyl isocyanate; 3-methoxyphenylisocyanate; 4-methoxyphenylisocyanate; ethyl 4-isocyanatobenzoate;2,6-dimethylphenylisocyante; 1-naphthylisocyanate;(naphthyl)ethylisocyantes; and the like, as well as mixtures thereof.Examples of diisocyanates include isophorone diisocyanate (IPDI);toluene diisocyanate (TDI); diphenylmethane-4,4′-diisocyanate (MDI);hydrogenated diphenylmethane-4,4′-diisocyanate (H12MDI); tetra-methylxylene diisocyanate (TMXDI); hexamethylene-1,6-diisocyanate (HDI);hexamethylene-1,6-diisocyanate; napthylene-1,5-diisocyanate;3,3′-dimethoxy-4,4′-biphenyldiisocyanate;3,3′-dimethyl-4,4′-bimethyl-4,4′-biphenyldiisocyanate; phenylenediisocyanate; 4,4′-biphenyldiisocyanate; trimethylhexamethylenediisocyanate; tetramethylene xylene diisocyanate;4,4′-methylenebis(2,6-diethylphenyl isocyanate);1,12-diisocyanatododecane; 1,5-diisocyanato-2-methylpentane;1,4-diisocyanatobutane; dimer diisocyanate and cyclohexylenediisocyanate and its isomers; uretidione dimers of HDI; and the like, aswell as mixtures thereof. Examples of triisocyanates or theirequivalents include the trimethylolpropane trimer of TDI, and the like,isocyanurate trimers of TDI, HDI, IPDI, and the like, and biuret trimersof TDI, HDI, IPDI, and the like, as well as mixtures thereof. Examplesof higher isocyanate functionalities include copolymers of TDI/HDI, andthe like, and MDI oligomers, as well as mixtures thereof.

Any suitable reaction condition for making urethane compounds bycondensing alcohols with isocyanates can be used to prepare polymericcolorants according to the present invention. Typically (although notnecessarily), the reaction is carried out at elevated temperatures (forexample, from about 60 to about 160° C.) in the presence of an optionalurethane reaction catalyst, such as dibutyl tindilaurate, bismuthtris-neodecanoate, cobalt benzoate, lithium acetate, stannous octoate,triethylamine, or the like. In a specific embodiment, the reactionconditions are conducted in an inert atmosphere, such as argon ornitrogen gas or other suitable gases, to prevent oxidizing or yellowingof the reaction products and to prevent undesirable side reactions. Thereaction can employ an inert solvent, such as toluene or the like, orcan be performed neat (i.e., without a solvent). The mole ratio ofreactants is adjusted so that the isocyanate functionalities arecompletely consumed in the reaction with a slight molar excess ofalcohol-substituted or amine-substituted antioxidant typicallyremaining. The reactants can be added together in any order and/or addedto the reaction as physical mixtures. See, for example, J. H. Saundersand K. C. Frisch's “Polyurethanes Part I, Chemistry” published byInterscience of New York, N.Y. in 1962 and Olin Chemicals' LUXATE® IMisophorone diisocyanate technical product information sheet, thedisclosures of each of which are totally incorporated herein byreference, which provide further explanation of this chemistry.

Colored anhydride resins having covalently bonded thereto a colorantaccording to the present invention are generally the reaction product ofa monomeric colorant according to the present invention and ananhydride. Colored anhydride resins having covalently bonded thereto acolorant according to the present invention can be prepared as disclosedin, for example, U.S. Pat. No. 6,110,264 and U.S. Pat. No. 6,322,624,the disclosures of each of which are totally incorporated herein byreference. Examples of suitable anhydrides include cyclic anhydrides,such as alkylsuccinic anhydrides, alkenylsuccinic anhydrides, and thelike, as well as mixtures thereof. Specific examples include (but arenot limited to) maleic anhydride, 2,3-diphenylmaleic anhydride,trimellitic anhydride, 2-phenylglutaric anhydride, homophthalicanhydride, isatoic anhydride, n-methylisatoic anhydride, 5-chloroisatoicanhydride, phthalic anhydride, 3,3′,4,4′-benzophenone tetracarboxylicdianhydride, 4-methylphthalic anhydride,4,4′-(hexafluoroisopropylidine)-diphthalic anhydride,3,6-difluorophthalic anhydride, 3,6-dichlorophthalic anhydride,4,5-dichlorophthalic anhydride, tetrafluorophthalic anhydride,tetrachlorophthalic anhydride, tetrabromophthalic anhydride,3-hydroxyphthalic anhydride, 1,2,4-benzenetricarboxylic anhydride,3-nitrophthalic anhydride, 4-nitrophthalic anhydride,1,2,4,5-benzenetetracarboxylic dianhydride, diphenic anhydride,1,8-naphthalic anhydride, 4-chloro-1,8-naphthalic anhydride,4-bromo-1,8-naphthalic anhydride, 4-amino-1,8-naphthalic anhydride,3-nitro-1,8-naphthalic anhydride, 4-nitro-1,8-naphthalic anhydride,4-amino-3,6,disulfo-1,6-disulfo-1,8-napthalic anhydride dipotassiumsalt, 1,4,5,8-naphthalenetetracarboxylic dianhydride,3,4,9,10-perylenetetracarboxylic dianhydride,cis-1,2,3,6-tetrahydrophthalic anhydride,cis-5-norbornene-endo-2,3dicarboxylic anhydride, endo-bicyco (2,2,2)oct-5-ene-2,3dicarboxylic anhydride, cantharidin,methyl-5-norbornene-2,3-dicarboxylic anhydride,exo-3,6,epoxy-1,2,3,6-tetrahydrophthalic anhydride,s-acetylmercaptosuccinic anhydride, diacetyl tartaric anhydride,bicyclo(2,2,2)octo-7-ene-2,3,5,6-tetracarboxylic dianhydride, citraconicanhydride, 2,3-dimethylmaleic anhydride, 1-cyclopentene-1,2-dicarboxylicanhydride, 3,4,5,6-tetrahydrophthalic anhydride, bromomaleic anhydride,dichloromaleic anhydride,1,4,6,7,7-hexachloro-5-norbornene-2,3-dicarboxylic anhydride,cis-aconitic anhydride, glutaric anhydride, 3-methylglutaric anhydride,2,2-dimethylglutaric anhydride, 3,3-dimethylglutaric anhydride,3-ethyl-3-methylglutaric anhydride, 3,3tetramethyleneglutaric anhydride,hexafluoroglutaric anhydride, 3,5-diacetyltetrahydropyran-2,4,6-trione,ethylenediaminetetraacetic dianhydride, diethylenetriaminepentaaceticdianhydride, diglycolic anhydride, succinic anhydride, methylsuccinicanhydride, 2,2-dimethylsuccinic anhydride, isobuteneylsuccinicanhydride, 2-octen-1-ylsuccinic anhydride, octadecenylsuccinicanhydride, 3-oxabicyclo(3,1,0) hexane-2,4-dione,cis-1,2-cyclohexanedicarboxylic anhydride,trans-1,2-cyclohexanedicarboxylic anhydride, hexahydro-4-methylphthalicanhydride, itaconic anhydride, 2-dodecen-1-ylsuccinic anhydride, and thelike, as well as mixtures thereof. For example, colored styrene-maleicanhydride resins having covalently bonded thereto a colorant accordingto the present invention are generally the reaction product of amonomeric colorant according to the present invention and styrene-maleicanhydride. Copolymers of anhydrides with styrene, butadiene,methoxyvinylether, ethylene, alpha-olefins, mixtures thereof, and thelike, are all suitable examples of polymeric materials with which themonomeric colorants of the present invention can be reacted to formcolored polymeric materials. Specific examples of suitable copolymersinclude (but are not limited to) poly(methyl vinyl ether-maleic acid),poly(acrylic acid-co-maleic acid), poly(vinylchloride-co-vinyl-acetate-co-maleic acid), poly(ethylene-maleicanhydride), poly(maleic anhydride-1-octadecene), poly(styrene-co-maleicanhydride), poly(methyl vinyl ether-maleic anhydride),poly(ethylene-co-ethyl acrylate-co-maleic anhydride),poly(ethylene-co-vinyl acetate)-graft-maleic anhydride,polyethylene-graft-maleic anhydride, polypropylene-graft-maleicanhydride, and the like, as well as mixtures thereof.

The monomeric precursor compounds and colorant compounds of the presentinvention, i.e., those containing only one moiety of the formula

have no more than one —OH, —SH, or —NHR″ group per molecule, wherein R″is a hydrogen atom, an alkyl group, an aryl group, an arylalkyl group,or an alkylaryl group. By this it is meant that, for example, if themolecule has one —OH group, it has no —SH groups, no —NHR″ groups, andno additional —OH groups. Because the colorant compounds of the presentinvention have one and only one of these groups, in some embodiments ofthe invention various advantages can be achieved. For example, whenthese colorants are reacted with other materials to form colored resins,there is no formation of products of undesirably high molecular weightand no undesired crosslinking. Some advantages are particularlydesirable for phase change ink applications. For example, when thesecolorants are reacted with other materials to form colored resins andwhen these colored resins are incorporated into a phase change ink,precipitation of the colorant from the ink is reduced; morespecifically, when multifunctional colorants, rather that the chainterminating colorants of the present invention, are employed inreactions of di- or tri-isocyanates and monohydric alcoholic species,some higher molecular weight species are produced which can be insolublein the ink base, often resulting or being manifested as a precipitate inthe prepared material and/or the final ink. In addition, when thesecolorants are reacted with other materials to form colored resins andwhen these colored resins are incorporated into a phase change ink,clogging of printheads and the printer failure accompanying suchclogging can be reduced.

The present invention is also directed to phase change inks. Anotherembodiment of the present invention is directed to a phase change inkcomprising a phase change carrier and a colorant compound comprising oneor more moieties of the formula

wherein R, R₁, R₂, R₃, and R₄ each, independently of the others, is analkyl group, an aryl group, an arylalkyl group, or an alkylaryl group,and wherein R, R₁, R₂, R₃, and R₄ each can be joined to a phenyl moietyto form a ring, each R′_(a), R′_(b), and R′_(c), independently of theothers, is a halogen atom, an alkyl group, an alkoxy group, a nitrilegroup, a nitro group, an amide group, or a sulfonamide group, z1, z2,and z3 each, independently of the others, is an integer of 0, 1, 2, 3,or 4, n is an integer representing the number of carbon atoms in eachrepeat alkylene oxide unit, x is an integer representing the number ofrepeat alkylene oxide units, D is an anion, and g is the charge on theanion, wherein, when the colorant compound contains exactly one of themoieties, the moiety contains no more than one —OH, —SH, or primary orsecondary amino group per molecule, and when the colorant compoundcontains more than one of the moieties, said moieties each contain no—OH groups, —SH groups, or primary or secondary amino groups. When onemoiety is present, the group is generally terminated by a hydrogen atomso that the polyalkyleneoxy chain has a terminal hydroxy group. When twoor more moieties are present, said moieties are linked by a central atomor group of atoms or bonded to a polymer.

In the direct printing mode, the phase change carrier composition in oneembodiment contains one or more materials that enable the phase changeink (1) to be applied in a thin film of uniform thickness on the finalrecording substrate (such as paper, transparency material, and the like)when cooled to ambient temperature after printing directly to therecording substrate, (2) to be ductile while retaining sufficientflexibility so that the applied image on the substrate will not fractureupon bending, and (3) to possess a high degree of lightness, chroma,transparency, and thermal stability.

In an offset printing transfer or indirect printing mode, the phasechange carrier composition in one embodiment exhibits not only thecharacteristics desirable for direct printing mode inks, but alsocertain fluidic and mechanical properties desirable for use in such asystem, as described in, for example, U.S. Pat. No. 5,389,958 thedisclosure of which is totally incorporated herein by reference.

When the phase change ink of the present invention comprises a coloredoligomer or polymer to which colorant molecules of the present inventionare covalently bonded, this colored oligomer or polymer can function asthe sole ink carrier. In addition, such a colored oligomer or polymercan be present in combination with another phase change ink carriercomposition. Further, when the phase change ink of the present inventioncomprises a colorant of the present invention having only one moiety ofthe formula

the colorant is generally present in combination with a phase change inkcarrier composition. Any desired or effective carrier composition can beused. Examples of suitable ink carrier materials include fatty amides,such as monoamides, tetraamides, mixtures thereof, and the like.Specific examples of suitable fatty amide ink carrier materials includestearyl stearamide, a dimer acid based tetra-amide that is the reactionproduct of dimer acid, ethylene diamine, and stearic acid, a dimer acidbased tetra-amide that is the reaction product of dimer acid, ethylenediamine, and a carboxylic acid having at least about 36 carbon atoms,and the like, as well as mixtures thereof. When the fatty amide inkcarrier is a dimer acid based tetra-amide that is the reaction productof dimer acid, ethylene diamine, and a carboxylic acid having at leastabout 36 carbon atoms, the carboxylic acid is of the general formula

wherein R is an alkyl group, including linear, branched, saturated,unsaturated, and cyclic alkyl groups, said alkyl group in one embodimenthaving at least about 36 carbon atoms, in another embodiment having atleast about 40 carbon atoms, said alkyl group in one embodiment havingno more than about 200 carbon atoms, in another embodiment having nomore than about 150 carbon atoms, and in yet another embodiment havingno more than about 100 carbon atoms, although the number of carbon atomscan be outside of these ranges. Carboxylic acids of this formula arecommercially available from, for example, Baker Petrolite, Tulsa, Okla.,and can also be prepared as described in Example 1 of U.S. Pat. No.6,174,937, the disclosure of which is totally incorporated herein byreference. Further information on fatty amide carrier materials isdisclosed in, for example, U.S. Pat. No. 4,889,560, U.S. Pat. No.4,889,761, U.S. Pat. No. 5,194,638, U.S. Pat. No. 4,830,671, U.S. Pat.No. 6,174,937, U.S. Pat. No. 5,372,852, U.S. Pat. No. 5,597,856, U.S.Pat. No. 6,174,937, and British Patent GB 2 238 792, the disclosures ofeach of which are totally incorporated herein by reference.

Also suitable as phase change ink carrier materials areisocyanate-derived resins and waxes, such as urethane isocyanate-derivedmaterials, urea isocyanate-derived materials, urethane/ureaisocyanate-derived materials, mixtures thereof, and the like. Furtherinformation on isocyanate-derived carrier materials is disclosed in, forexample, U.S. Pat. No. 5,750,604, U.S. Pat. No. 5,780,528, U.S. Pat. No.5,782,966, U.S. Pat. No. 5,783,658, U.S. Pat. No. 5,827,918, U.S. Pat.No. 5,830,942, U.S. Pat. No. 5,919,839, U.S. Pat. No. 6,255,432, U.S.Pat. No. 6,309,453, British Patent GB 2 294 939, British Patent GB 2 305928, British Patent GB 2 305 670, British Patent GB 2 290 793, PCTPublication WO 94/14902, PCT Publication WO 97/12003, PCT Publication WO97/13816, PCT Publication WO 96/14364, PCT Publication WO 97/33943, andPCT Publication WO 95/04760, the disclosures of each of which aretotally incorporated herein by reference.

Mixtures of fatty amide materials and isocyanate-derived materials canalso be employed as the ink carrier composition for inks of the presentinvention.

Additional suitable phase change ink carrier materials for the presentinvention include paraffins, microcrystalline waxes, polyethylene waxes,ester waxes, amide waxes, fatty acids, fatty alcohols, fatty amides andother waxy materials, sulfonamide materials, resinous materials madefrom different natural sources (such as, for example, tall oil rosinsand rosin esters), and many synthetic resins, oligomers, polymers andcopolymers, such as ethylene/vinyl acetate copolymers, ethylene/acrylicacid copolymers, ethylene/vinyl acetate/acrylic acid copolymers,copolymers of acrylic acid with polyamides, and the like, ionomers, andthe like, as well as mixtures thereof. One or more of these materialscan also be employed in a mixture with a fatty amide material and/or anisocyanate-derived material.

In one specific embodiment, the phase change ink carrier comprises theink-carrier comprises (a) a polyethylene wax, present in the ink in anamount in one embodiment of at least about 25 percent by weight of theink, in another embodiment of at least about 30 percent by weight of theink, and in yet another embodiment of at least about 37 percent byweight of the ink, and in one embodiment of no more than about 60percent by weight of the ink, in another embodiment of no more thanabout 53 percent by weight of the ink, and in yet another embodiment ofno more than about 48 percent by weight of the ink, although the amountcan be outside of these ranges; (b) a stearyl stearamide wax, present inthe ink in an amount in one embodiment of at least about 8 percent byweight of the ink, in another embodiment of at least about 10 percent byweight of the ink, and in yet another embodiment of at least about 12percent by weight of the ink, and in one embodiment of no more thanabout 32 percent by weight of the ink, in another embodiment of no morethan about 28 percent by weight of the ink, and in yet anotherembodiment of no more than about 25 percent by weight of the ink,although the amount can be outside of these ranges; (c) a dimer acidbased tetra-amide that is the reaction product of dimer acid, ethylenediamine, and a carboxylic acid derivative of a long chain alcohol havinggreater than thirty six carbon atoms, present in the ink in an amount inone embodiment of at least about 10 percent by weight of the ink, inanother embodiment of at least about 13 percent by weight of the ink,and in yet another embodiment of at least about 16 percent by weight ofthe ink, and in one embodiment of no more than about 32 percent byweight of the ink, in another embodiment of no more than about 27percent by weight of the ink, and in yet another embodiment of no morethan about 22 percent by weight of the ink, although the amount can beoutside of these ranges; (d) a urethane resin derived from the reactionof two equivalents of hydroabietyl alcohol and one equivalent ofisophorone diisocyanate, present in the ink in an amount in oneembodiment of at least about 6 percent by weight of the ink, in anotherembodiment of at least about 8 percent by weight of the ink, and in yetanother embodiment of at least about 10 percent by weight of the ink,and in one embodiment of no more than about 16 percent by weight of theink, in another embodiment of no more than about 14 percent by weight ofthe ink, and in yet another embodiment of no more than about 12 percentby weight of the ink, although the amount can be outside of theseranges; (e) a urethane resin that is the adduct of three equivalents ofstearyl isocyanate and a glycerol-based alcohol, present in the ink inan amount in one embodiment of at least about 2 percent by weight of theink, in another embodiment of at least about 3 percent by weight of theink, and in yet another embodiment of at least about 4.5 percent byweight of the ink, and in one embodiment of no more than about 13percent by weight of the ink, in another embodiment of no more thanabout 10 percent by weight of the ink, and in yet another embodiment ofno more than about 7.5 percent by weight of the ink, although the amountcan be outside of these ranges; and (f) an antioxidant, present in theink in an amount in one embodiment of at least about 0.01 percent byweight of the ink, in another embodiment of at least about 0.05 percentby weight of the ink, and in yet another embodiment of at least about0.1 percent by weight of the ink, and in one embodiment of no more thanabout 1 percent by weight of the ink, in another embodiment of no morethan about 0.5 percent by weight of the ink, and in yet anotherembodiment of no more than about 0.3 percent by weight of the ink,although the amount can be outside of these ranges.

The ink carrier is present in the phase change ink of the presentinvention in any desired or effective amount, in one embodiment of atleast about 0.1 percent by weight of the ink, in another embodiment ofat least about 50 percent by weight of the ink, and in yet anotherembodiment of at least about 90 percent by weight of the ink, and in oneembodiment of no more than about 99 percent by weight of the ink, inanother embodiment of no more than about 98 percent by weight of theink, and in yet another embodiment of no more than about 95 percent byweight of the ink, although the amount can be outside of these ranges.

The phase change inks of the present invention contain a colorantcompound comprising one or more moieties of the formula

wherein R, R₁, R₂, R₃, and R₄ each, independently of the others, is analkyl group, an aryl group, an arylalkyl group, or an alkylaryl group asfurther defined hereinabove, and wherein R, R₁, R₂, R₃, and R₄ each canbe joined to a phenyl moiety to form a ring, each R′_(a), R′_(b), andR′_(c), independently of the others, is a halogen atom, an alkyl group,an alkoxy group, a nitrile group, a nitro group, an amide group, or asulfonamide group as further defined hereinabove, z1, z2, and z3 each,independently of the others, is an integer of 0, 1, 2, 3, or 4, n is aninteger representing the number of carbon atoms in each repeat alkyleneoxide unit as further defined hereinabove, x is an integer representingthe number of repeat alkylene oxide units as further definedhereinabove, D is an anion as further defined hereinabove, and g is thecharge on the anion, wherein, when the colorant compound containsexactly one of the moieties, the moiety contains no more than one —OH,—SH, or primary or secondary amino group per molecule, and when thecolorant compound contains more than one of the moieties, said moietieseach contain no —OH groups, —SH groups, or primary or secondary aminogroups. This colorant is present in the ink in any desired or effectiveamount to obtain the desired color or hue, in one embodiment of at leastabout 1 percent by weight of the ink, in another embodiment of at leastabout 2 percent by weight of the ink, and in yet another embodiment ofat least about 3 percent by weight of the ink, and in one embodiment ofno more than about 20 percent by weight of the ink, in anotherembodiment of no more than about 13 percent by weight of the ink, and inyet another embodiment of no more than about 6 percent by weight of theink, although the amount can be outside of these ranges. The colorantaccording to the present invention can either be the sole colorant inthe ink or can be present in combination with other colorants, such asdyes, pigments, mixtures thereof, and the like.

The inks of the present invention can also optionally contain anantioxidant. The optional antioxidants of the ink compositions protectthe images from oxidation and also protect the ink components fromoxidation during the heating portion of the ink preparation process.Specific examples of suitable antioxidants include NAUGUARD® 524,NAUGUARD® 76, and NAUGUARD® 512, commercially available from UniroyalChemical Company, Oxford, Conn., IRGANOX® 1010, commercially availablefrom Ciba Geigy, and the like. When present, the optional antioxidant ispresent in the ink in any desired or effective amount, in one embodimentof at least about 0.01 percent by weight of the ink, in anotherembodiment of at least about 0.1 percent by weight of the ink, and inyet another embodiment of at least about 1 percent by weight of the ink,and in one embodiment of no more than about 20 percent by weight of theink, in another embodiment of no more than about 5 percent by weight ofthe ink, and in yet another embodiment of no more than about 3 percentby weight of the ink, although the amount can be outside of theseranges.

The inks of the present invention can also optionally contain aviscosity modifier. Examples of suitable viscosity modifiers includealiphatic ketones, such as stearone, and the like. When present, theoptional viscosity modifier is present in the ink in any desired oreffective amount, in one embodiment of at least about 0.1 percent byweight of the ink, in another embodiment of at least about 1 percent byweight of the ink, and in yet another embodiment of at least about 10percent by weight of the ink, and in one embodiment of no more thanabout 99 percent by weight of the ink, in another embodiment of no morethan about 30 percent by weight of the ink, and in yet anotherembodiment of no more than about 15 percent by weight of the ink,although the amount can be outside of these ranges.

Other optional additives to the inks include clarifiers, such as UNIONCAMP® X37-523-235 (commercially available from Union Camp), in an amountin one embodiment of at least about 0.01 percent by weight of the ink,in another embodiment of at least about 0.1 percent by weight of theink, and in yet another embodiment of at least about 5 percent by weightof the ink, and in one embodiment of no more than about 98 percent byweight of the ink, in another embodiment of no more than about 50percent by weight of the ink, and in yet another embodiment of no morethan about 10 percent by weight of the ink, although the amount can beoutside of these ranges, tackifiers, such as FORAL® 85, a glycerol esterof hydrogenated abietic (rosin) acid (commercially available fromHercules), FORAL® 105, a pentaerythritol ester of hydroabietic (rosin)acid (commercially available from Hercules), CELLOLYN® 21, ahydroabietic (rosin) alcohol ester of phthalic acid (commerciallyavailable from Hercules), ARAKAWA KE-311 Resin, a triglyceride ofhydrogenated abietic (rosin) acid (commercially available from ArakawaChemical Industries, Ltd.), synthetic polyterpene resins such as NEVTAC®2300, NEVTAC®100, and NEVTAC® 80 (commercially available from NevilleChemical Company), WINGTACK® 86, a modified synthetic polyterpene resin(commercially available from Goodyear), and the like, in an amount inone embodiment of at least about 0.1 percent by weight of the ink, inanother embodiment of at least about 5 percent by weight of the ink, andin yet another embodiment of at least about 10 percent by weight of theink, and in one embodiment of no more than about 98 percent by weight ofthe ink, in another embodiment of no more than about 75 percent byweight of the ink, and in yet another embodiment of no more than about50 percent by weight of the ink, although the amount can be outside ofthese range, adhesives, such as VERSAMID® 757, 759, or 744 (commerciallyavailable from Henkel), in an amount in one embodiment of at least about0.1 percent by weight of the ink, in another embodiment of at leastabout 1 percent by weight of the ink, and in yet another embodiment ofat least about 5 percent by weight of the ink, and in one embodiment ofno more than about 98 percent by weight of the ink, in anotherembodiment of no more than about 50 percent by weight of the ink, and inyet another embodiment of no more than about 10 percent by weight of theink, although the amount can be outside of these ranges, plasticizers,such as UNIPLEX® 250 (commercially available from Uniplex), thephthalate ester plasticizers commercially available from Monsanto underthe trade name SANTICIZER®, such as dioctyl phthalate, diundecylphthalate, alkylbenzyl phthalate (SANTICIZER® 278), triphenyl phosphate(commercially available from Monsanto), KP-140®, a tributoxyethylphosphate (commercially available from FMC Corporation), MORFLEX® 150, adicyclohexyl phthalate (commercially available from Morflex ChemicalCompany Inc.), trioctyl trimellitate (commercially available fromEastman Kodak Co.), and the like, in an amount in one embodiment of atleast about 0.1 percent by weight of the ink, in another embodiment ofat least about 1 percent by weight of the ink, and in yet anotherembodiment of at least about 2 percent by weight of the ink, and in oneembodiment of no more than about 50 percent by weight of the ink, inanother embodiment of no more than about 30 percent by weight of theink, and in yet another embodiment of no more than about 10 percent byweight of the ink, although the amount can be outside of these ranges,and the like.

The ink compositions of the present invention in one embodiment havemelting points of no lower than about 50° C., in another embodiment ofno lower than about 70° C., and in yet another embodiment of no lowerthan about 80° C., and have melting points in one embodiment of nohigher than about 160° C., in another embodiment of no higher than about140° C., and in yet another embodiment of no higher than about 100° C.,although the melting point can be outside of these ranges.

The ink compositions of the present invention generally have meltviscosities at the jetting temperature (in one embodiment no lower thanabout 75° C., in another embodiment no lower than about 100° C., and inyet another embodiment no lower than about 120° C., and in oneembodiment no higher than about 180° C., and in another embodiment nohigher than about 150° C., although the jetting temperature can beoutside of these ranges) in one embodiment of no more than about 30centipoise, in another embodiment of no more than about 20 centipoise,and in yet another embodiment of no more than about 15 centipoise, andin one embodiment of no less than about 2 centipoise, in anotherembodiment of no less than about 5 centipoise, and in yet anotherembodiment of no less than about 7 centipoise, although the meltviscosity can be outside of these ranges.

The ink compositions of the present invention can be prepared by anydesired or suitable method. For example, the ink ingredients can bemixed together, followed by heating, to a temperature in one embodimentof at least about 100° C., and in one embodiment of no more than about140° C., although the temperature can be outside of these ranges, andstirring until a homogeneous ink composition is obtained, followed bycooling the ink to ambient temperature (typically from about 20 to about25° C.). The inks of the present invention are solid at ambienttemperature.

The inks of the present invention can be employed in apparatus fordirect printing ink jet processes and in indirect (offset) printing inkjet applications. Another embodiment of the present invention isdirected to a process which comprises incorporating an ink of thepresent invention into an ink jet printing apparatus, melting the ink,and causing droplets of the melted ink to be ejected in an imagewisepattern onto a recording substrate. A direct printing process is alsodisclosed in, for example, U.S. Pat. No. 5,195,430, the disclosure ofwhich is totally incorporated herein by reference. Yet anotherembodiment of the present invention is directed to a process whichcomprises incorporating an ink of the present invention into an ink jetprinting apparatus, melting the ink, causing droplets of the melted inkto be ejected in an imagewise pattern onto an intermediate transfermember, and transferring the ink in the imagewise pattern from theintermediate transfer member to a final recording substrate. An offsetor indirect printing process is also disclosed in, for example, U.S.Pat. No. 5,389,958, the disclosure of which is totally incorporatedherein by reference. In one specific embodiment, the printing apparatusemploys a piezoelectric printing process wherein droplets of the ink arecaused to be ejected in imagewise pattern by oscillations ofpiezoelectric vibrating elements. Inks of the present invention can alsobe employed in other hot melt printing processes, such as hot meltacoustic ink jet printing, hot melt thermal ink jet printing, hot meltcontinuous stream or deflection ink jet printing, and the like. Phasechange inks of the present invention can also be used in printingprocesses other than hot melt ink jet printing processes.

Any suitable substrate or recording sheet can be employed, includingplain papers such as XEROX® 4024 papers, XEROX® Image Series papers,Courtland 4024 DP paper, ruled notebook paper, bond paper, silica coatedpapers such as Sharp Company silica coated paper, JuJo paper, HammermillLaserprint Paper, and the like, transparency materials, fabrics, textileproducts, plastics, polymeric films, inorganic substrates such as metalsand wood, and the like.

Specific embodiments of the invention will now be described in detail.These examples are intended to be illustrative, and the invention is notlimited to the materials, conditions, or process parameters set forth inthese embodiments. All parts and percentages are by weight unlessotherwise indicated.

EXAMPLE I Phase Separation of N-Ethyl Aniline Ethoxylate

To a 100 milliliter beaker equipped with a magnetic stirrer was addedabout 50 milliliters of POE(10) N-ethyl aniline, of the formula

(obtained from Henkel Corp, Mauldin, S.C.) and about 65 milliliters ofdeionized water. The mixture was placed on a magnetic stirring hot plateand stirring and heating were initiated. When the temperature reached90° C., the beaker was removed from heat and stirring and was allowed tocool slowly. After several minutes, separation of layers began to occur,and after about 2 hours, the temperature had returned to roomtemperature and the separation was complete. A separation of the twolayers was visually observed, and separation of the layers was performedwith a separatory funnel.

Acetylation/Protection

To a 1,000 milliliter flask equipped with a vacuum adapter and magneticstirrer was added about 400.0 grams of POE(10) N-ethyl aniline. Theflask was placed in a 140° C. oil bath under vacuum with stirring forabout 1 hour. The vacuum source was then removed and about 88.3milliliters of acetic anhydride (obtained from Aldrich Chemical Co.,Milwaukee, Wis.) and 10 drops of 1-methylimidazole (obtained fromAldrich Chemical Co.) were added to the flask. A nitrogen atmosphere andreflux condenser were then introduced, and the mixture was allowed toheat at 140 to 150° C. for about 4 hours. Thereafter, the condenser andnitrogen atmosphere were removed and a vacuum was gradually applied withthe temperature at about 130° C. to remove excess acetic-anhydride andacetic acid (generated as a reaction byproduct). Infrared spectroscopyshowed that the OH band (3200-3600 cm⁻¹) in the POE(10) N-ethyl anilinehad disappeared 20 in the product, and a carbonyl band (1720-1770 cm⁻¹)had appeared in the product, indicating the success of the acetylationreaction.

Formylation

The acetylated product thus formed was transferred to a 1,000 milliliter4-necked flask equipped with a Trubore stirrer, constant pressureaddition funnel, nitrogen atmosphere, and thermometer. About 128.0 gramsof dimethyl formamide (obtained from Aldrich Chemical Co.) was added tothe acetylated product, stirring was initiated, and the mixture wascooled to about 0° C. About 160.0 grams of POCl₃ (obtained from AldrichChemical Co.) were added to the addition funnel and added dropwise tothe reaction mixture at a rate to keep the temperature below 5° C.(about 5 hours). The reaction mixture was then stirred for 1 additionalhour at 5° C., set at room temperature overnight, and then heated to 80°C. for about 2 hours. Thereafter, about 500 grams of 50 percent sodiumhydroxide (solid material obtained from Aldrich Chemical Co.) in waterwas added slowly at a rate to keep the temperature below 80° C. Uponaddition of all of the sodium hydroxide solution, the mixture was pouredinto a 1,000 milliliter separatory funnel and allowed to phase separate.The bottom layer (comprising salt and water) was then drained anddiscarded.

Deacetylation/Deprotection

The acetylated and formylated product thus formed was then transferredback into a 1,000 milliliter 4-necked flask equipped with a Truborestirrer, nitrogen atmosphere, and thermocouple temperature controller.About 280 grams of 50 percent sodium hydroxide (obtained from AldrichChemical Co.) in water and about 90 grams of 50 percent potassiumhydroxide in water (solid material obtained from Aldrich Chemical Co.)were added, and the reaction mixture was heated to 100° C. andmaintained at that temperature for about 3 hours. Thereafter, about 72grams of 50 percent potassium hydroxide (obtained from Aldrich ChemicalCo.) in water and 600 grams of deionized water were added, and heatingwas continued at 100° C. for an additional hour. The product mixture wasthen poured into a 2,000 milliliter separatory funnel and allowed tophase separate overnight. The water/salt layer was then removed,yielding the formylated hydroxy-terminated product of the formula

EXAMPLE II Acetylation/Protection

To a 1,000 milliliter flask equipped with a vacuum adapter and magneticstirrer was added about 200.0 grams of a random POE (3.5) POP (6.5)N-ethyl aniline, of the formula

wherein 3.5 represents the average number of repeat polyoxyethyleneunits per molecule and 6.5 represents the average number of repeatpolyoxypropylene units per molecule, and wherein the polyoxyethylene andpolyoxypropylene units are randomly mixed within the polyoxyalkylenechain (obtained as SO-7864 from Henkel Corp., Mauldin, S.C.). The flaskwas placed in a 140° C. oil bath under vacuum with stirring for about 1hour. The vacuum source was then removed and about 36.5 grams of aceticanhydride (obtained from Aldrich Chemical Co., Milwaukee, Wis.) and 10drops of 1-methylimidazole (obtained from Aldrich Chemical Co.) wereadded to the flask. A nitrogen atmosphere and reflux condenser were thenintroduced, and the mixture was allowed to heat at 130 to 135° C. forabout 3 hours. Thereafter, a vacuum was gradually applied with thetemperature at about 130° C. to remove excess acetic acid (generated asa reaction byproduct) and acetic anhydride. Infrared spectroscopy showedthat the OH band (3200-3600 cm⁻¹) in the POE/POP N-ethyl aniline haddisappeared in the product, and a carbonyl band (1720-1770 cm⁻¹) hadappeared in the product, indicating the success of the acetylationreaction.

Formylation

About 195.0 grams of the acetylated product thus formed was transferredto a 1,000 milliliter 4-necked flask equipped with a Trubore stirrer,constant pressure addition funnel, nitrogen atmosphere, and thermometer.About 51.0 grams of dimethyl formamide (obtained from Aldrich ChemicalCo.) was added to the acetylated product, stirring was initiated, andthe mixture was cooled to about 0° C. About 63.8 grams of POCl₃(obtained from Aldrich Chemical Co.) were added to the addition funneland added dropwise to the reaction mixture at a rate to keep thetemperature below 5° C. (about 3 hours). The reaction mixture was thenstirred for 0.5 additional hour at 5° C., set at room temperatureovernight, and then heated to 80° C. for about 2 hours. Thereafter,about 275 grams of deionized water was added and enough 50 percentsodium hydroxide solution in water (solid sodium hydroxide obtained fromAldrich Chemical Co.) was added slowly at a rate to keep the temperaturebelow 80° C. Upon addition of all of the sodium hydroxide solution, themixture was poured into a 1,000 milliliter separatory funnel and allowedto phase separate. The bottom layer (comprising salt and water) was thendrained and discarded.

Deacetylation/Deprotection

The acetylated and formylated product thus formed was then transferredback into a 1,000 milliliter 4-necked flask equipped with a TEFLON®coated magnet on a stirring hot plate. About 70 grams of sodiumhydroxide and 23 grams of potassium hydroxide (obtained from AldrichChemical Co.) was dissolved in 400 milliliters of deionized water, andthe reaction mixture was heated to 100° C. and maintained at thattemperature for about 2 hours. The product mixture was then poured intoa 2,000 milliliter separatory funnel and allowed to phase separateovernight. The water/salt layer was then removed. The product layer wastransferred to a 2 liter beaker, 400 grams of deionized water wereadded, and the mixture was neutralized to a pH of about 7 with sulfuricacid (obtained from Aldrich Chemical Co.). The mixture was then heatedto about 70° C. and transferred back to the separatory funnel andallowed to separate overnight. The water/salt layer was discarded,yielding the formylated hydroxy-terminated product of the formula

The product was stripped of any remaining residual water on a rotaryevaporator. Infrared spectroscopy showed that the OH band (3200-3600cm⁻¹) in the POE(3.5) POP (6.5) N-ethyl aniline was again present in theproduct, and a carbonyl band (1720-1770 cm⁻¹) of the formyl group waspresent in the product.

EXAMPLE III Monohydroxyl Triphenylmethane Polyoxyalkylene TPM VioletColorant

To a 100 milliliter 1-necked round bottom flask equipped with a magneticstirrer was added 20.0 grams (about 0.029 moles) of the para-formylatedPOE(3.5) POP(6.5) N-ethyl aniline adduct prepared in Example II, 8.85grams of N,N-diethylaniline (obtained from Aldrich Chemical Co.), 0.6grams of urea (obtained from Aldrich Chemical Co.), and 1.5 grams ofconcentrated H₂SO₄ (obtained from Aldrich Chemical Co.). The flask wasplaced into a 100° C. oil bath, stirring was commenced, and the mixturewas allowed to heat/stir for 3 hours. After 3 hours, 3.1 grams ofbenzoquinone (obtained from Aldrich Chemical Co.) and 2.0 grams of waterwere added to the reaction mixture and stirring/heating was continuedfor 2 hours, at which time the flask was removed from the heat and theviolet liquid product was allowed to cool to room temperature. Theproduct at this point was a viscous violet liquid consistent with theformula

EXAMPLE IV

The process of Example III is repeated except that the formylatedhydroxy-terminated product prepared as described in Example I is usedinstead of the formylated hydroxy-terminated product prepared asdescribed in Example II. It is believed that the resulting product willhave a structure similar to that of the colorant of Example III exceptthat the product will be of the formula

EXAMPLE V Reaction Product of Benzophenonetetracarboxylic DianhydrideOctochenol Ethoxylate, and Violet TPM Monohydroxyl Colorant

To a 1,000 milliliter three-neck resin kettle equipped with a Truborestirrer, N₂ inlet, and thermocouple-temperature controller is added150.0 grams (0.93 equivalents) of benzophenonetetracarboxylicdianhydride (available from Aldrich Chemical Co., Milwaukee, Wis.) and211.6 grams (0.83 equivalents) of IGEPAL CA-210 (octylphenol ethoxylate,available from Rhone-Poulenc Co., Cranbury, N.J. Note: TRITON X15octylphenol ethoxylate, available from Union Carbide Chemicals andPlastics Company Inc., Danbury, Conn., can be directly substituted forIGEPAL CA-210 in this reaction.). The reaction mixture is heated to 150°C. with stirring under nitrogen. After 1.0 hours at 150° C. thetemperature is increased to 170° C. and held at that temperature for 3.5hours. A violet monohydroxyl polyalkyleneoxy colorant (103.0 grams,0.098 equivalents) prepared as described in Example III is then addedand allowed to react for 3 hours. The final magenta colored resinproduct is then poured into aluminum molds and allowed to cool andharden.

EXAMPLE VI

The colored resin prepared in Example V (20.5 grams) is combined with58.7 grams of stearyl stearamide wax (KEMAMIDE® S-180, available fromCrompton Corporation, Greenwich, Conn.), 20.5 grams of glycerol ester ofhydrogenated abietic (rosin) acid (KE-100, available from ArakawaChemical Industries, Ltd.), and 0.2 gram of NAUGUARD® 445 antioxidant(available from Uniroyal Chemical Co., Middlebury, Conn.). Theingredients are heated to 115° C. until molten, mixed, filtered througha disc filter, poured into sticks, and used to generate prints in aXEROX® PHASER 860 printer.

EXAMPLE VII Reaction Product of Octylphenol Ethoxylate. IsophoroneDiisocyanate, and Violet TPM Monohydroxyl Polyoxyalkylene Colorant

525.0 grams (4.73 equivalents) of isophorone diisocyanate (availablefrom Bayer Corp., Pittsburgh, Pa.) and 1.5 grams of dibutyltindilauratecatalyst (available from Aldrich Chemical Co., Milwaukee, Wis.),followed by 1,150 grams (4.52 equivalents) of octylphenol ethoxylate(IGEPAL CA-210 octylphenol ethoxylate, available from Rhone-Poulenc Co.,Cranbury, N.J.), are added to a 3,000 milliliter three-neck resin kettleequipped with a Trubore stirrer, N₂ atmosphere inlet, and athermocouple-temperature controller. The reaction mixture is heated to135° C. with stirring under nitrogen. After 2.0 hours at 135° C., 216.0grams (0.210 equivalents) of violet monohydroxyl polyoxyalkylenecolorant prepared as described in Example III above are added and thereaction mixture is heated for approximately 2 hours. An additional 11.0grams (0.0433 equivalents) of octylphenol ethoxylate are then added andthe reaction mixture is heated at 150° C. for approximately 2 hours. AnFT-IR of the product is obtained to ensure that all of the isocyanate(NCO) functionality has been consumed. The absence (disappearance) of apeak at about 2285 cm⁻¹ (NCO) and the appearance (or increase inmagnitude) of peaks at about 1740-1680 cm⁻¹ and about 1540-1530 cm⁻¹corresponding to urethane frequencies are used to confirm that theisocyanate has been consumed. The diurethane reaction product is thenpoured into aluminum molds and allowed to cool and harden.

EXAMPLE VIII

In a stainless steel beaker are combined 500 grams of stearyl stearamidewax (KEMAMIDE® S-180, available from Crompton Corporation, Greenwich,Conn.), 125 grams of UNIREZ 2970 tetra-amide resin (available from UnionCamp, Wayne, N.J.), 208 grams of the colored resin prepared as describedin Example VII, and 1.6 grams of NAUGUARD® 445 antioxidant (availablefrom Uniroyal Chemical Co., Middlebury, Conn.). The materials are meltedtogether at a temperature of about 140° C. in an oven, then blended bystirring in a temperature controlled mantle at about 115° C. for about0.5 hour. After stirring, the resulting ink is filtered through a heatedMott apparatus (available from Mott Metallurgical) using #3 Whatmanfilter paper and a pressure of about 15 psi. The filtered phase changeink is then poured into molds, allowed to solidify to form ink sticks,and used to generate prints in a XEROX® PHASER 860 printer.

EXAMPLE IX Reaction Product of Styrene-Maleic Anhydride Polymer withNeodol 1-3 and Violet TPM Monohydroxyl Polyoxyalkylene Colorant

To a 500 milliliter three-neck resin kettle equipped with a TEFLON®coated magnet, oil bath, and condenser is added 14.0 grams (0.068equivalents) of styrene-maleic anhydride polymer (SMA 1000, availablefrom Atochem Inc., Malvern, Pa.), 15.9 grams (0.052 equivalents) of analcohol of the formula C₁₁H₂₂—O—(CH₂CH₂O)_(n)H wherein n has an averagevalue of 3 (NEODOL 1-3, available from Shell Chemical Company, Houston,Tex.), 0.017 equivalents of a violet monohydroxyl polyoxyalkylenecolorant prepared as described in Example III, about 250 grams ofacetonitrile (available from Aldrich Chemical Co., Milwaukee, Wis.), and2 drops of 1-methylimidazole catalyst (available from Aldrich ChemicalCo.). The reaction mixture is heated with stirring to reflux and held atthat state for 2 days. After 2 days, the acetonitrile is removed bydistillation. The violet viscous colored product still in the flask isthen placed in a vacuum oven to remove any residue of acetonitrile.

EXAMPLE X

To a 100 milliliter beaker equipped with magnetic stir was added about 8grams of the violet material prepared as described in Example IX and 35milliliters of concentrated ammonia solution. Stirring was continueduntil all the solid material dissolved. About 2 milliliters of thisaqueous solution was placed on the platen of a K-proofer and prints weremade. The prints were allowed to dry and tested for washfastness. Nobleeding of color was observed.

Other embodiments and modifications of the present invention may occurto those of ordinary skill in the art subsequent to a review of theinformation presented herein; these embodiments and modifications, aswell as equivalents thereof, are also included within the scope of thisinvention.

The recited order of processing elements or sequences, or the use ofnumbers, letters, or other designations therefor, is not intended tolimit a claimed process to any order except as specified in the claimitself.

1. A colorant compound of the formula

wherein R, R₁, R₂, R₃, and R₄ each, independently of the others, is analkyl group, including saturated, unsaturated, cyclic, and unsubstitutedalkyl groups, and wherein hetero atoms either may or may not be presentin the alkyl group, an aryl group, including unsubstituted andsubstituted aryl groups, and wherein hetero atoms either may or may notbe present in the aryl group, an arylalkyl group, includingunsubstituted and substituted arylalkyl groups, and wherein hetero atomseither may or may not be present in either or both of the alkyl portionand the aryl portion of the arylalkyl group, or an alkylaryl group,including unsubstituted and substituted alkylaryl groups, and whereinhetero atoms either may or may not be present in either or both of thealkyl portion and the aryl portion of the alkylaryl group, and whereinR, R₁, R₂, R₃, and R₄ each can be joined to a phenyl moiety to form aring, each R′_(a), R′_(b), and R′_(c), independently of the others, is ahalogen atom, an alkyl group, an alkoxy group, a nitrile group, a nitrogroup, an amide group, or a sulfonamide group, z1, z2, and z3 each,independently of the others, is an integer of 0, 1, 2, 3, or 4, n is aninteger representing the number of carbon atoms in each repeat alkyleneoxide unit, x is an integer representing the number of repeat alkyleneoxide units, D is an anion, and g is the charge on the anion, whereinsaid colorant has no more than one —OH, —SH, or primary or secondaryamino group per molecule.
 2. A colorant compound according to claim 1wherein R is an alkyl group with at least one carbon atom and with nomore than about 50 carbon atoms, an aryl group with at least about 5carbon atoms and with no more than about 50 carbon atoms, an arylalkylgroup with at least about 6 carbon atoms and with no more than about 50carbon atoms, or an alkylaryl group with at least about 6 carbon atomsand with no more than about 50 carbon atoms.
 3. A colorant compoundaccording to claim 1 wherein R is ethyl.
 4. A colorant compoundaccording to claim 1 wherein n is at least about 2 and wherein n is nomore than about
 18. 5. A colorant compound according to claim 1 whereinn is no more than about
 4. 6. A colorant compound according to claim 1wherein x is at least about 2 and wherein x is no more than about 100.7. A colorant compound according to claim 1 wherein x is at least about5 and wherein x is no more than about
 20. 8. A colorant compoundaccording to claim 1 wherein R′_(a), R′_(b), and R′_(c) each,independently of the others, is a fluorine atom, a chlorine atom, abromine atom, an iodine atom, an alkyl group with at least one carbonatom and with no more than about 25 carbon atoms, an alkoxy group withat least one carbon atom and with no more than about 25 carbon atoms, anitrile group, a nitro group, an amide group of the formula

wherein R_(m) is a hydrogen atom, an alkyl group, including saturated,unsaturated, cyclic, and unsubstituted alkyl groups, and wherein heteroatoms either may or may not be present in the alkyl group, with at least1 carbon atom and with no more than about 50 carbon atoms, an arylgroup, unsubstituted and substituted aryl groups, and wherein heteroatoms either may or may not be present in the aryl group, with at least5 carbon atoms and with no more than about 50 carbon atoms, an arylalkylgroup, including unsubstituted and substituted arylalkyl groups, andwherein hetero atoms either may or may not be present in either or bothof the alkyl portion and the aryl portion of the arylalkyl group, withat least about 6 carbon atoms and with no more than about 50 carbonatoms, or an alkylaryl group, including unsubstituted and substitutedalkylaryl groups, and wherein hetero atoms either may or may not bepresent in either or both of the alkyl portion and the aryl portion ofthe alkylaryl group, with at least about 6 carbon atoms and with no morethan about 50 carbon atoms, or a sulfonamide group of the formula

wherein R_(p) is a hydrogen atom, an alkyl group, including saturated,unsaturated, cyclic, and unsubstituted alkyl groups, and wherein heteroatoms either may or may not be present in the alkyl group, with at least1 carbon atom and with no more than about 50 carbon atoms, an arylgroup, including unsubstituted and substituted aryl groups, and whereinhetero atoms either may or may not be present in the aryl group, with atleast 5 carbon atoms and with no more than about 50 carbon atoms, anarylalkyl group, including unsubstituted and substituted arylalkylgroups, and wherein hetero atoms either may or may not be present ineither or both of the alkyl portion and the aryl portion of thearylalkyl group, with at least about 6 carbon atoms and with no morethan about 50 carbon atoms, or an alkylaryl group, includingunsubstituted and substituted alkylaryl groups, and wherein hetero atomseither may or may not be present in either or both of the alkyl portionand the aryl portion of the alkylaryl group, with at least about 6carbon atoms and with no more than about 50 carbon atoms.
 9. A colorantcompound according to claim 1 wherein R₁, R₂, R₃, and R₄ each,independently of the others, is an alkyl group with at least one carbonatom and with no more than about 50 carbon atoms, an aryl group with atleast about 5 carbon atoms and with no more than about 50 carbon atoms,an arylalkyl group with at least about 6 carbon atoms and with no morethan about 50 carbon atoms, or an alkylaryl group with at least about 6carbon atoms and with no more than about 50 carbon atoms.
 10. A colorantcompound according to claim 1 wherein R₁, R₂, R₃, and R₄ are each alkylgroups containing hetero atoms or alkyl groups containing no heteroatoms.
 11. A colorant compound according to claim 1 wherein z1, z2, andz3 are all
 0. 12. A colorant compound of the formula

wherein R, R₁, R₂, R₃, and R₄ each, independently of the others, is analkyl group, including saturated, unsaturated, cyclic, and unsubstitutedalkyl groups, and wherein hetero atoms either may or may not be presentin the alkyl group, and wherein R, R₁, R₂, R₃, and R₄ each can be joinedto a phenyl moiety to form a ring, n is an integer representing thenumber of carbon atoms in each repeat alkylene oxide unit and has anaverage value of 2 or 3, x is an integer representing the number ofrepeat alkylene oxide units and is at least about 5 and no more thanabout 20, D is an anion, and g is the charge on the anion, wherein saidcolorant has no more than one —OH, —SH, or primary or secondary aminogroup per molecule.
 13. A colorant compound according to claim 12wherein R contains no hetero atoms.
 14. A colorant compound according toclaim 12 wherein R is ethyl.
 15. A colorant compound according to claim12 wherein R₁, R₂, R₃, and R₄ each, independently of the others, have atleast one carbon atom and have no more than about 50 carbon atoms.
 16. Acolorant compound according to claim 12 wherein at least some of R₁, R₂,R₃, and R₄ contain hetero atoms.
 17. A colorant compound according toclaim 12 wherein at least some of R₁, R₂, R₃, and R₄ contain no heteroatoms.
 18. A colorant compound according to claim 12 wherein g is 2 andD is sulfate.
 19. A colorant compound according to claim 12 wherein D isphosphate.
 20. A colorant compound according to claim 12 wherein n is 2.